Abstract
Reversible Addition−Fragmentation Chain-Transfer (RAFT) polymerization of styrene (St), vinyl benzyl chloride (vbc), tert-butyl methacrylate (tertBMA) and n-butyl methacrylate (nBMA) was investigated using carboxylic acid functionalized trithiocarbonate (R2). A series of random copolymer of styrene and vinyl benzyl chloride was prepared in order to control chloromethyl functionality in the copolymer, via RAFT polymerization. Addition to this, first-order kinetic behavior of the RAFT polymerization of vbc using R2 was also evaluated. A novel series of amphiphilic copolymers based on polyethylene glycol (PEG) with molar masses of 500 and 2000 g/mol, functionalized polyvinyl benzyl chloride (Pvbc) were obtained via the Williamson-ether-synthesis. As chloromethyl functionality increases, the introduced PEG increases. Fractional precipitation, thermal properties and water uptakes of the amphiphilic polymer samples were evaluated. The new polymers can be the promising materials with high aqueous solubility capacity.
Similar content being viewed by others
References
Kotani Y, Kato M, Kamigaito M, Sawamoto M (1996) Living Radical Polymerization of Alkyl Methacrylates with Ruthenium Complex and Synthesis of Their Block Copolymers1. Macromolecules 29:6979–6982
Hazer B (1989) Synthesis and characterization of block copolymers. Handbook of polymer science and technology, vol 1. Marcel Dekker, Inc, pp 133–176
Hillmyer MA, Bates FS (1996) Synthesis and Characterization of Model Polyalkane−Poly(ethylene oxide) Block Copolymers. Macromolecules 29(22):6994–7002
Hazer B, Baysal BM (1986) Preparation of block copolymers using a new polymeric peroxycarbamate. Polymer 27:961–968
İ. Çakmak, B. Hazer, Y. Yağcı, Eur Polym J 1991, 27, 101, Polymerization of acrylamide by the redox system cerium(IV) with poly (ethylene glycol) with azo groups, 103
Roos SG, Muller AHE, Matyjaszewski K (1999) Copolymerization ofn-Butyl Acrylate with Methyl Methacrylate and PMMA Macromonomers: Comparison of Reactivity Ratios in Conventional and Atom Transfer Radical Copolymerization. Macromolecules 32:8331–8335
Arkin AH, Hazer B (2002) Chemical Modification of Chlorinated Microbial Polyesters. Biomacromolecules 3(6):1327–1335
Cakir N, Yavuzarslan M, Durmaz H, Hizal G, Tunca U (2013) Heterograft brush copolymers via romp and triple click reaction strategies involving CuAAC, diels-alder, and nitroxide radical coupling reactions. J Polym Sci, Part A: Polym Chem 51:899–907
Hazer B (1995) Grafting on polybutadiene with macro or macromonomer initiators containing poly(ethylene glycol) units. Macromol Chem Phys 196:1945–1952
Hazer B (1991) Synthesis of styrene-tetrahydrofuran branched block copolymers. Eur Polym J 27:975–978
Baek K-Y, Kamigaito M, Sawamoto M (2001) Core-Functionalized Star Polymers by Transition Metal-Catalyzed Living Radical Polymerization. 1. Synthesis and Characterization of Star Polymers with PMMA Arms and Amide Cores1. Macromolecules 34:7629–7635
Kul D, Volga C, Yilmaz SS, Hazer B (2002) Initiation system effects in the cationic copolymerization of tetrahydrofuran (THF). Polym Bull 49:25–32
Weber C, Wagner M, Baykal D, Hoeppener S, Paulus RM, Festag G, Altuntas E, Schacher FH, Schubert US (2013) Easy Access to Amphiphilic Heterografted Poly(2-oxazoline) Comb Copolymers. Macromolecules 46:5107–5116
Fruth A, Klapper M, Müllen K (2010) Synthesis and Characterization of Amphiphilic Polyelectrolyte Brush Copolymers Based on Poly(2,7-carbazole). Macromolecules 43:467–472
Lee H-i, Pietrasik J, Sheiko SS, Matyjaszewski K (2010) Stimuli-responsive molecular brushes. Prog Polym Sci 35:24–44
Balcı M, Allı A, Hazer B, Guven O, Cavicchi K, Cakmak M (2010) Synthesis and characterization of novel comb-type amphiphilic graft copolymers containing polypropylene and polyethylene glycol. Polym Bull 64:691–705
Şanal T, Koçak İ, Hazer B (2017) Synthesis of comb-type amphiphilic graft copolymers derived from chlorinated poly(ɛ-caprolactone) via click reaction. Polym Bull 74:977–995
M. Mullner, J. Yuan, S. Weiss, A. Walther, M. Fortsch, M. Drechsler, A. H. E. Muller, J Am Chem Soc 2010, 132, 16587, Water-Soluble Organo−Silica Hybrid Nanotubes Templated by Cylindrical Polymer Brushes, 16592
Hazer DB, Sakar M, Dere Y, Ziyal Mİ, Hazer B (2016) Antimicrobial Effect of Polymer-Based Silver Nanoparticle Coated Pedicle Screws. Spine 41(6):E323–E329
Hazer B (1992). Makromol Chem 193:1081–1086
Simon PFW, Muller AHE (2001) Synthesis of Hyperbranched and Highly Branched Methacrylates by Self-Condensing Group Transfer Copolymerization. Macromolecules 34:6206–6213
Jin M, Lu R, Bao CY, Xu TH, Zhao YY (2004) Synthesis and characterization of hyperbranched azobenzene-containing polymers via self-condensing atom transfer radical polymerization and copolymerization. Polymer 45:1125–1131
Voit BI, Lederer A (2009) Hyperbranched and Highly Branched Polymer Architectures—Synthetic Strategies and Major Characterization Aspects. Chem Rev 109(11):5924–5973
Yıldız U, Hazer B (2000) Dispersion redox copolymerization of methyl methacrylate with macromonomeric azoinitiator as a macrocrosslinker. Polymer 41:539–544
Yıldız U, Hazer B, Tauer K (2012) Tailoring polymer architectures with macromonomer azoinitiators. Polym Chem 3:1107
Hadjichristidis N, Pitsikalis M, Pispas S, Iatrou H (2012). Chem Rev 101:3747
Castillo RV, Müller AJ (2009) Crystallization and morphology of biodegradable or biostable single and double crystalline block copolymers. Prog Polym Sci 34:516–560
Riess G (2003) Micellization of block copolymers. Prog Polym Sci 28:1107–1170
Barouti G, Jaffredo CG, Guillaume SM (2017) Advances in drug delivery systems based on synthetic poly(hydroxybutyrate) (co)polymers. Prog Polym Sci 73:1–31
Hirao A, Hayashi M, Loykulnant S, Sugiyama K, Ryu SW, Haraguchi N, Matsuo A, Higashihara T (2005) Precise syntheses of chain-multi-functionalized polymers, star-branched polymers, star-linear block polymers, densely branched polymers, and dendritic branched polymers based on iterative approach using functionalized 1,1-diphenylethylene derivatives. Prog Polym Sci 30:111–182
Ishizu K, Tusubaki K, Mori A, Uchida S (2003) Architecture of nanostructured polymers. Prog Polym Sci 28:27–54
Davis KA, Charleux B, Matyjaszewski K (2000) Preparation of block copolymers of polystyrene and poly (t-butyl acrylate) of various molecular weights and architectures by atom transfer radical polymerization. J Polym Sci: Part A: Polym Chem 38:2274–2283
Matyjaszewski K, Xia J (2001) Atom Transfer Radical Polymerization. Chem Rev 101:2921–2990
Ouchi M, Terashima T, Sawamoto M (2009) Transition Metal-Catalyzed Living Radical Polymerization: Toward Perfection in Catalysis and Precision Polymer Synthesis. Chem Rev 109:4963–5050
Ozturk T, Yılmaz SS, Hazer B, Menceloglu YZ (2010) ATRP of methyl methacrylate initiated with a bifunctional initiator bearing bromomethyl functional groups: Synthesis of the block and graft copolymers. J Polym Sci: Part A: Polym Chem 48:1364–1373
Braunecker WA, Matyjaszewski K (2007) Controlled/living radical polymerization: Features, developments, and perspectives. Prog Polym Sci 32:93–146
H, Arslan (2012) Polymerization/book 1 “block and graft copolymerization by controlled/ “living”radical polymerization methods” edited by Ailton De Souza Gomes. INTECH 2012:279–320. https://doi.org/10.5772/45970
Arslan H, Zırtıl O, Bütün V (2013) The synthesis and solution behaviors of novel amphiphilic block copolymers based on d-galactopyranose and 2-(dimethylamino)ethyl methacrylate. Eur Polym J 49:4118–4129
Chiefari H, Chong YK, Ercole F, Krstina J, Jeffery J, Le TPT, Mayadunne RTA, Meijs GF, Moad CL, Moad G, Rizzardo E, Thang SH (1998). Macromolecules 31:5559
G. Moad, C. Barner-Kowollik, The mechanism and kinetics of the RAFT process. In Handbook of RAFT polymerization; Barner Kowollik, C., Ed., Wiley-VCH: Weinheim, Germany, 2008
Vandenbergh J, Schweitzer-Chaput B, Klussmann M, Junkers T (2016) Acid-Induced Room Temperature RAFT Polymerization: Synthesis and Mechanistic Insights. Macromolecules 49:4124–4135
Öztürk T, Göktaş M, Hazer B (2010). J Appl Polym Sci 117:1638
Ozturk T, Atalar MN, Goktas M, Hazer B (2013) One-step synthesis of block-graft copolymers via simultaneous reversible-addition fragmentation chain transfer and ring-opening polymerization using a novel macroinitiator. J Polym Sci: Part A: Polym Chem 51:2651–2659
Hawker CJ, Bosman AW, Harth E (2001) New Polymer Synthesis by Nitroxide Mediated Living Radical Polymerizations. Chem Rev 101:3661–3688
Sciannamea V, Jerome R, Detrembleur C (2008) In-Situ Nitroxide-Mediated Radical Polymerization (NMP) Processes: Their Understanding and Optimization. Chem Rev 108:1104–1126
Allı A, Allı S, Becer CR, Hazer B (2016) Nitroxide-mediated copolymerization of styrene and pentafluorostyrene initiated by polymeric linoleic acid. Eur J Lipid Sci Technol 118:279–287
Saka Y, Zetterlund PB, Okubo M (2007) Gel formation and primary chain lengths in nitroxide-mediated radical copolymerization of styrene and divinylbenzene in miniemulsion. Polymer 48:1229–1236
Tasdelen MA, Yagci Y, Demirel AL, Biedron T, Kubisa P (2007) Synthesis and Characterization of Block-Graft Copolymers [poly(epichlorohydrin-b-styrene)-g-poly(methyl methacrylate)] by Combination of Activated Monomer Polymerization, NMP and ATRP. Polym Bull 58:653–663
Förster S, Antonietti M (1998) Amphiphilic Block Copolymers in Structure-Controlled Nanomaterial Hybrids. Adv Mater 10:195–217
Pispas S, Hadjichristidis N (2003) Aggregation Behavior of Poly(butadiene-b-ethylene oxide) Block Copolymers in Dilute Aqueous Solutions: Effect of Concentration, Temperature, Ionic Strength, and Type of Surfactant. Langmuir 19:48–54
B. Hazer, Int. J. Polym. Sci. 2010. Article number: 423460, https://doi.org/10.1155/2010/423460
I. Cakmak, B. Hazer, Y. Yagci, Eur Polym J 1991, 27, 101, Polymerization of acrylamide by the redox system cerium(IV) with poly (ethylene glycol) with azo groups, 103
Arslan H, Pfaff A, Lu Y, Stepanek P, Müller AHE (2014) Stimuli-Responsive Spherical Brushes Based onD-Galactopyranose and 2-(Dimethylamino)ethyl Methacrylate. Macromol Biosci 14:81–91
Xu R, Winnik MA, Hallet FR, Riess G, Croucher MD (1991) Light-scattering study of the association behavior of styrene-ethylene oxide block copolymers in aqueous solution. Macromolecules 24:87–93
Hansen NML, Gerstenberg M, Haddleton DM, Hvilsted S (2008) Synthesis, characterization, and bulk properties of amphiphilic copolymers containing fluorinated methacrylates from sequential copper-mediated radical polymerization. J Polym Sci A Polym Chem 46:8097–8111
Bütün V, Bannister I, Billingham NC, Sherrington DC, Armes SP (2005) Synthesis and Characterization of Branched Water-Soluble Homopolymers and Diblock Copolymers Using Group Transfer Polymerization. Macromolecules 38:4977–4982
Minoda M, Sawamoto M, Higashimura T (1990) Amphiphilic block copolymers of vinyl ethers by living cationic polymerization. 3. Anionic macromolecular amphiphiles with pendant carboxylate anions. Macromolecules 23:1897–1901
Hazer DB, Mut M, Dinçer N, Sarıbaş Z, Hazer B, Özgen T (2012) The efficacy of silver-embedded polypropylene-grafted polyethylene glycol-coated ventricular catheters on prevention of shunt catheter infection in rats. Childs Nerv Syst 28:839–846
Erciyes AT, Erim M, Hazer B, Yağcı Y (1992). Angew Macromol Chem 200:163–171
Şanal T, Oruç O, Öztürk T, Hazer B (2015). J Polym Res 22(3):1
Ferguson CJ, Hughes RJ, Nguyen D, Pham BTT, Gilbert RG, Serelis AK, Such CH, Hawkett BS (2005) Ab Initio Emulsion Polymerization by RAFT-Controlled Self-Assembly§. Macromolecules 38:2191–2204
Wendler U, Bohrisch J, Jaeger W, Rother G, Dautzenberg H (1998) Amphiphilic cationic block copolymers via controlled free radical polymerization. Macromol Rapid Commun 19:185–192
Li Y, Jackson AC, Beyer FL, Knauss DM (2014) Poly(2,6-dimethyl-1,4-phenylene oxide) Blended with Poly(vinylbenzyl chloride)-b-polystyrene for the Formation of Anion Exchange Membranes. Macromolecules 47:6757–6767
Faghihi F, Hazendonk P (2017) RAFT polymerization, characterization, and post-polymerization modification of a copolymer of vinylbenzyl chloride: Towards thiolate functionalized copolymers. Polymer 128:31–39
Lin C, Gitsov I (2010) Synthesis and Physical Properties of Reactive Amphiphilic Hydrogels Based on Poly(p-chloromethylstyrene) and Poly(ethylene glycol): Effects of Composition and Molecular Architecture. Macromolecules 43:3256–3267
Save M, Manguian M, Chassenieux C, Charleux B (2005) Synthesis by RAFT of Amphiphilic Block and Comblike Cationic Copolymers and Their Use in Emulsion Polymerization for the Electrosteric Stabilization of Latexes. Macromolecules 38:280–289
Dong Z, Fu Z, Shi Y, Yang W (2012) Synthesis and characterization of Q-PEO-b-PVBC and Q-PEO-b-(PVBC-grad-PS) combined RAFT polymerization and post-polymerization quaternization. J Polym Res 19:9953
Tsai T-H, Ertem SP, Maes AM, Seifert S, Herring AM, Coughlin EB (2015) Thermally Cross-Linked Anion Exchange Membranes from Solvent Processable Isoprene Containing Ionomers. Macromolecules 48:655–662
Liu Y, Cavicchi KA (2009) Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization with a Polymeric RAFT Agent Containing Multiple Trithiocarbonate Groups. Macromol Chem Phys 210:1647–1653
Lu F, Luo Y, Li B, Zhao Q, Schork FJ (2010) Synthesis of Thermo-Sensitive Nanocapsules via Inverse Miniemulsion Polymerization Using a PEO−RAFT Agent. Macromolecules 43:568–571
Guo M, Zhang M, He D, Hu J, Wang X, Gong C, Xie X, Xue Z (2017) Comb-like solid polymer electrolyte based on polyethylene glycol-grafted sulfonated polyether ether ketone. Electrochim Acta 255:396–404
Zhang Q, Ye J, Lu Y, Nie T, Xie D, Song Q, Chen H, Zhang G, Tang Y, Wu C, Xie Z (2008) Synthesis, Folding, and Association of Long Multiblock (PEO23-b-PNIPAM124)750Chains in Aqueous Solutions. Macromolecules 41:2228–2234
Lai JT, Filla D, Shea R (2002) Functional Polymers from Novel Carboxyl-Terminated Trithiocarbonates as Highly Efficient RAFT Agents. Macromolecules 35:6754–6756
Gitsov I, Wooley KL, Hawker CJ, Ivanova PT, Frechet JMJ (1993) Synthesis and properties of novel linear-dendritic block copolymers. Reactivity of dendritic macromolecules toward linear polymers. Macromolecules 26:5621–5627
Couture G, Améduri B (2012) Kinetics of RAFT homopolymerisation of vinylbenzyl chloride in the presence of xanthate or trithiocarbonate. Eur Polym J 48:1348–1356
Zhang C, Zhou Y, Liu Q, Li S, Perrier S, Zhao Y (2011) Facile Synthesis of Hyperbranched and Star-Shaped Polymers by RAFT Polymerization Based on a Polymerizable Trithiocarbonate. Macromolecules 44:2034–2049
Wu B, Lenz RW, Hazer B (1999) Polymerization of Methyl Methacrylate and Its Copolymerization with ε-Caprolactone Catalyzed by Isobutylalumoxane Catalyst. Macromolecules 32:6856–6859
Hazer B, Akyol E (2016) Efficiency of Gold Nano Particles on the Autoxidized Soybean Oil Polymer: Fractionation and Structural Analysis. J Amer Oil Chem Soc 93:201–213
Arslan H, Hazer B, Higashihara T, Hirao A (2006) Synthesis of asymmetric star-branched block copolymers based on PS, PTHF, and PMMA by combination of cationic ring opening polymerization and redox polymerization methods. J Appl Polym Sci 102:516–522
Abbasian M, Masoumi B, Masoudi A, Rashidzadeh B (2014) Synthesis and Characterization of Poly Chloromethylstyrene TiO2-Nanocomposite Through a Simple Method via Reversible Addition-Fragmentation Transfer Polymerization. Polym-Plast Technol Eng 53:1150–1159
Weimer MW, Frechet JMJ, Gitsov I (1998) Importance of active-site reactivity and reaction conditions in the preparation of hyperbranched polymers by self-condensing vinyl polymerization: Highly branchedvs. linear poly[4-(chloromethyl)styrene] by metal-catalyzed ?living? radical polymerization. J Polym Sci: Part A: Polym Chem 36:955–970
Acknowledgments
This work was supported by the Bülent Ecevit University Research Funds (#BEU-2017-72118496-01) and Kapadokya University KÜN.2018-BAGP-001. This paper has been proofread by Bülent Ecevit University Article Proofreading and Editing Office.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The Authors declare that there is no conflict of interest.
Additional information
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Hazer, B., Arslan, H., Senemoğlu, Y. et al. Synthesis of block/graft copolymers based on vinyl benzyl chloride via reversible addition fragmentation chain transfer (RAFT) polymerization using the carboxylic acid functionalized Trithiocarbonate. J Polym Res 26, 101 (2019). https://doi.org/10.1007/s10965-019-1763-z
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s10965-019-1763-z