Synlett 2021; 32(05): 497-501
DOI: 10.1055/s-0037-1610764
cluster
The Power of Transition Metals: An Unending Well-Spring of New Reactivity

Advances in Internal Plasticization of PVC: Copper-Mediated Atom-Transfer Radical Polymerization from PVC Defect Sites To Form Acrylate Graft Copolymers

Longbo Li
a  Department of Chemistry and Biochemistry, University of California, Santa Cruz, 1156 High Street, Santa Cruz, CA 95064, USA
,
Yanika Schneider
b  EAG Laboratories, 810 Kifer Rd, Sunnyvale, CA 94086, USA
,
Adrienne B. Hoeglund
c  EAG Laboratories, 2672 Metro Blvd, Maryland Heights, MS 63043, USA
,
Rebecca Braslau
a  Department of Chemistry and Biochemistry, University of California, Santa Cruz, 1156 High Street, Santa Cruz, CA 95064, USA
› Author Affiliations
We gratefully acknowledge research funding from the National Science Foundation (DMR-1404550).


Dedicated to Barry Trost: celebrating a lifetime of exploring the beauty of transition-metal catalysis in organic synthesis.

Abstract

Internally plasticized PVC copolymers were prepared by grafting PVC with butyl acrylate and 2-(2-ethoxyethoxy)ethyl acrylate by atom-transfer radical polymerization, resulting in well-behaved polymers with a wide range of glass transition temperatures (–54 °C to 54 °C). When the grafted side chains made up more than 50% of the polymer by weight, the glass transition temperatures were below 0 °C. The covalent attachment of the plasticizing grafts requires one simple procedure starting from commercial PVC, making this strategy an industrially relevant and environmentally friendly alternative to the use of conventional small-molecule plasticizers.

Supporting Information



Publication History

Received: 07 December 2020

Accepted: 15 January 2021

Publication Date:
12 February 2021 (online)

© 2021. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 
  • References and Notes

  • 1 Carroll WF, Johnson RW, Moore SS, Paradis RA. In Applied Plastics Engineering Handbook, 2nd ed. Kutz M. Elsevier; Cambridge: 2017. DOI: Chap. 4, 73
  • 2 Larsen ST. In Handbook of Plasticizers, 3rd ed. Wypych G. ChemTec Publishing; Toronto: 2017. DOI: Chap. 17, 681
  • 3 Mijangos C, Martinez A, Michel A. Eur. Polym. J. 1986; 22: 417
    • 4a Navarro R, Pérez Perrino M, Gómez Tardajos M, Reinecke H. Macromolecules 2010; 43: 2377
    • 4b Navarro R, Perrino PM, García C, Elvira C, Gallardo A, Reinecke H. Polymers (Basel, Switz.) 2016; 8: 152
    • 4c Navarro R, Pérez Perrino M, García C, Elvira C, Gallardo A, Reinecke H. Macromolecules 2016; 49: 2224
    • 4d Navarro R, Gacal T, Ocakoglu M, García C, Elvira C, Gallardo A, Reinecke H. Macromol. Rapid Commun. 2017; 38: 1600734
    • 5a Jia P, Hu L, Yang X, Zhang M, Shang Q, Zhou Y. RSC Adv. 2017; 7: 30101
    • 5b Jia P, Hu L, Shang Q, Wang R, Zhang M, Zhou Y. ACS Sustainable Chem. Eng. 2017; 5: 6665
    • 5c Jia P, Zhang M, Hu L, Song F, Feng G, Zhou Y. Sci. Rep. 2018; 8: 1589
  • 6 Earla A, Braslau R. Macromol. Rapid Commun. 2014; 35: 666
  • 7 Yang P, Yan J, Sun H, Fan H, Chen Y, Wang F, Shi B. RSC Adv. 2015; 5: 16980
  • 8 Demirci G, Tasdelen MA. Eur. Polym. J. 2015; 66: 282
  • 9 Lee KW, Chung JW, Kwak S.-Y. Macromol. Rapid Commun. 2016; 37: 2045
  • 10 Jia P, Hu L, Feng G, Bo C, Zhang M, Zhou Y. Mater. Chem. Phys. 2017; 190: 25
  • 11 Jia P, Wang R, Hu L, Zhang M, Zhou Y. Pol. J. Chem. Technol. 2017; 19: 16
  • 12 Earla A, Li L, Costanzo P, Braslau R. Polymer 2017; 109: 1
  • 13 Chu H, Ma J. Korean J. Chem. Eng. 2018; 35: 2296
  • 14 Higa CM, Tek AT, Wojtecki RJ, Braslau R. J. Polym. Sci., Part A: Polym. Chem. 2018; 56: 2397
  • 15 Li L, Tek AT, Wojtecki RJ, Braslau R. J. Polym. Sci., Part A: Polym. Chem. 2019; 57: 1821
  • 16 Jia P, Ma Y, Feng G, Hu L, Zhou Y. J. Cleaner Prod. 2019; 227: 662
  • 17 Coelho JF. J, Carreira M, Popov AV, Gonçalves PM. O. F, Gil MH. Eur. Polym. J. 2006; 42: 2313
  • 18 Coelho JF. J, Carreira M, Gonçalves PM. O. F, Popov AV, Gil MH. J. Vinyl Addit. Technol. 2006; 12: 156
  • 19 Sun Z, Choi B, Feng A, Moad G, Thang SH. Macromolecules 2019; 52: 1746
  • 20 Rezende TC, Abreu CM. R, Fonseca AC, Higa CM, Li L, Serra AC, Braslau R, Coelho JF. J. Polymer 2020; 196: 122473
    • 21a Matyjaszewski K, Xia J. Chem. Rev. 2001; 101: 2921
    • 21b Matyjaszewski K. Macromolecules 2012; 45: 4015
    • 21c Matyjaszewski K, Tsarevsky NV. J. Am. Chem. Soc. 2014; 136: 6513
  • 22 Paik H, Gaynor SG, Matyjaszewski K. Macromol. Rapid Commun. 1998; 19: 47
  • 23 Percec V, Asgarzadeh F. J. Polym. Sci., Part A: Polym. Chem. 2001; 39: 1120
  • 24 Percec V, Cappotto A, Barboiu B. Macromol. Chem. Phys. 2002; 203: 1674
  • 25 Bicak N, Ozlem M. J. Polym. Sci., Part A: Polym. Chem. 2003; 41: 3457
  • 26 Bicak N, Karagoz B, Emre D. J. Polym. Sci., Part A: Polym. Chem. 2006; 44: 1900
  • 27 Coşkun M, Barim G, Demirelli KA. J. Macromol. Sci., Part A: Pure Appl. Chem. 2007; 44: 475
  • 28 Ahn SH, Seo JA, Kim JH, Ko Y, Hong SU. J. Membr. Sci. 2009; 345: 128
  • 29 Patel R, Patel M, Ahn SH, Sung YK, Lee H.-K, Kim JH, Sung J.-S. Mater. Sci. Eng., C 2013; 33: 1662
  • 30 Fang L.-F, Matsuyama H, Zhu B.-K, Zhao S. J. Appl. Polym. Sci. 2018; 135: 45832
  • 31 Lanzalaco S, Galia A, Lazzano F, Mauro RR, Scialdone O. J. Polym. Sci., Part A: Polym. Chem. 2015; 53: 2524
  • 32 Huang Z, Feng C, Guo H, Huang X. Polym. Chem. 2016; 7: 3034
  • 33 Liu K, Pan P, Bao Y. RSC Adv. 2015; 5: 94582
  • 34 Wypych G. PVC Degradation and Stabilization . 3rd ed. Wypych G.; ChemTec Publishing; Toronto: 2015: 1
  • 35 Li, L.; Schneider, Y.; Hoeglund, A. B.; Braslau, R. submitted for publication.
  • 36 PVC-g-50%PBA-co-50%P2EEA (Table [1], Entry 5); Typical Procedure A 10 mL Schlenk flask was charged with PVC (500.7 mg, 8.011 mmol) and DMF (3 mL), and the mixture was stirred and slightly warmed to fully dissolve the polymer. BA (1.43 mL, 9.97 mmol) and 2EEA (1.85 mL, 9.99 mmol) were then added to the solution. A 2 mL vial was charged with CuBr (34.22 mg, 0.2386 mmol) and 0.75 mL of DMF to form a suspension, which was transferred to the PVC solution by pipette. Residual CuBr was washed into the PVC solution with DMF (0.25 mL), and PMDETA (50 μL, 0.24 mmol) was added. The mixture was degassed by four freeze–pump–thaw cycles, then heated to 100 °C and stirred under N2 for 2 h. An aliquot of the crude reaction mixture was taken and analyzed by 1H NMR with CDCl3 as solvent (conversion = 60 wt%). The polymer was precipitated by adding the mixture to MeOH (200 mL), followed by stirring for 30 min. The MeOH was decanted and the residual polymer was left overnight in additional MeOH (100 mL) without stirring. The solution phase was decanted and the polymer was dried under mild vacuum. The polymer, containing residual solvent, was washed with additional MeOH (5 mL), and the solvent was decanted. The product was thoroughly dried under vacuum to give a pale-green pliable polymer; yield: 1.5567 g (percentage wt. of plasticizer by gravimetry: 68%). FTIR (neat): 2974 (m, alkane C–H), 2931 (m, alkane C–H), 2873 (m, alkane C–H), 1736 (s, ester C=O), 1169 (s, ester C–O), 1119 (m, ether C–O). 1H NMR (500 MHz, CDCl3): δ = 4.65–4.54 (br m), 4.54–4.38 (br m), 4.38–4.25 (br m), 4.25–4.12 (br m), 4.12–3.93 (br m), 3.72–3.65 (br m), 3.65–3.60 (br m), 3.60–3.55 (br m), 3.52 (q, J = 7.0 Hz), 2.49–2.23 (br m), 2.23–1.97 (br m), 1.97–1.81 (br m), 1.74–1.57 (br m), 1.51–1.43 (br m), 1.43–1.29 (br m), 1.21 (t, J = 7.0 Hz), 0.94 (t, J = 7.3 Hz). From 1H NMR integration: (PBA + P2EEA)/PVC = 0.9:1.0; PBA/P2EEA = 1.0:1.0; plasticizer = 60 wt%.
  • 37 Wypych G. PVC Degradation and Stabilization, 3rd ed. Wypych G. ChemTec Publishing; Toronto: 2015. DOI: Chap. 4, 79