Abstract
This chapter highlights the application of controlled/“living” polymerization (CLP) techniques in automated parallel synthesizers for both optimizing reaction parameters as well as preparing copolymer libraries. Special attention is given to the use of CLP techniques for constructing well-defined copolymer libraries. Furthermore, alternative strategies for the preparation of block copolymer libraries are discussed.
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- AA:
-
Acrylic acid
- AcBr:
-
Acetyl bromide
- AcCl:
-
Acetyl chloride
- AcI:
-
Acetyl iodide
- AFM:
-
Atomic force microscopy
- AIBN:
-
α,α-Azobisisobutyronitrile
- Amor:
-
N-Acryoyl morpholine
- ATRP:
-
Atom transfer radical polymerization
- BEB:
-
(1-Bromo ethyl) benzene
- bpy:
-
4, 4′-Dialkyl substituted bipyridine
- BrEBiB:
-
2-Bromo-2-methylpropanoyl bromide
- CBDB:
-
2-Cyano-2-butyl dithio benzoate
- CLP:
-
Controlled/“living” polymerization
- CROP:
-
Cationic ring opening polymerization
- CRP:
-
Controlled radical polymerization
- CTA:
-
Chain transfer agent
- DMA:
-
N,N-Dimethyl acrylamide
- DMAc:
-
N,N-Dimethyl acetamide
- DMAEMA:
-
N,N-Dimethyl aminoethyl acrylamide
- DMF:
-
N,N-Dimethyl formamide
- DP:
-
Degree of polymerization
- DSC:
-
Differential scanning calorimetry
- EEA:
-
1-Ethoxy ethyl acrylate
- EBIB:
-
Ethyl-2-bromo-iso-butyrate
- EtOx:
-
2-Ethyl-2-oxazoline
- GC:
-
Gas chromatography
- HPA:
-
2-Hydoxypropyl acrylate
- iPrOx:
-
2-iso-Propyl-2-oxazoline
- LCST:
-
Lower critical solution temperature
- MA:
-
Methyl acrylate
- MAA:
-
Methacrylic acid
- MADIX:
-
Macromolecular design via the interchange of xanthates
- MBP:
-
Methyl bromo propionate
- MMA:
-
Methyl methacrylate
- MeOMA:
-
2-Methoxyethyl 2-methylacrylate
- MeO2MA:
-
2-(2-Methoxyethoxy)ethyl 2-methylacrylate
- MeOx:
-
2-Methyl-2-oxazoline
- M n :
-
Number average molar mass
- nBA:
-
n-Butyl acrylate
- NIPAM:
-
N-Isopropyl acrylamide
- NMP:
-
Nitroxide mediated polymerization
- NMR:
-
Nuclear magnetic resonance
- NonOx:
-
2-Nonyl-2-oxazoline
- OEGMA:
-
Oligo(ethyleneglycol) methyl ether methacrylate
- OEGEMA:
-
Oligo(ethylene glycol) ethyl ether methacrylate
- PAA:
-
Poly(acrylic acid)
- PDI:
-
Polydispersity index
- PEEA:
-
Poly(1-ethoxyethyl acrylate)
- PEG:
-
Poly(ethyleneglycol)
- PEO:
-
Poly(ethylene oxide)
- PheOx:
-
2-Phenyl-2-oxazoline
- PDMAEMA:
-
Poly(N,N-dimethyl aminoethyl methacrylate)
- PMA:
-
Poly(methyl acrylate)
- PMMA:
-
Poly(methyl methacrylate)
- PnBA:
-
Poly(n-butyl acrylate)
- PSt:
-
Poly(styrene)
- PtBA:
-
Poly(tert-butyl acrylate)
- RAFT:
-
Reversible addition-fragmentation chain transfer
- SEC:
-
Size exclusion chromatography
- s-BuLi:
-
sec-Butyllithium
- SPE:
-
Solid phase extraction
- SoyOx:
-
2-“Soyalkyl”-2-oxazoline
- St:
-
Styrene
- tBA:
-
tert-Butyl acrylate
- TEMPO:
-
2,2,6,6-Tetramethyl-1-piperidinyloxy stable radical
- Tg :
-
Glass transition temperature
- TGA:
-
Thermal gravimetric analysis
- TsCl:
-
p-Toluene sulfonyl chloride
References
Kamigaito M, Ando T, Sawamoto M (2001) Metal-catalyzed living radical polymerization. Chem Rev 101:3689–3745
Matyjaszewski K, Xia JH (2001) Atom transfer radical polymerization. Chem Rev 101: 2921–2990
Hawker CJ, Bosman AW, Harth E (2001) New polymer synthesis by nitroxide mediated living radical polymerizations. Chem Rev 101:3661–3688
Moad G, Rizzardo E, Thang SH (2005) Living radical polymerization by the RAFT process. Aust J Chem 58:379–410
Hadjichristidis N, Pitsikalis M, Pispas S et al. (2001) Polymers with complex architecture by living anionic polymerization. Chem Rev 101:3747–3792
de Gans BJ, Duineveld P, Schubert US (2004) Ink-jet printing of polymers: state of the art and future developments. Adv Mater 16:203–213
Tekin E, Smith PJ, Schubert US (2008) Inkjet printing of functional materials: from polymers to nanoparticles and molecules. Soft Matter 4:703–713
de Gans BJ, Schubert US (2003) Ink-jet printing of polymer microarrays and libraries: requirements, possibilities and available instrumentation. Macromol Rapid Commun 24:659–666
Meredith JC, Smith AP, Karim A et al. (2000) Combinatorial materials science for polymer thin-film dewetting. Macromolecules 33:9747–9756
Smith AP, Douglas JF, Meredith JC et al. (2001) High-throughput characterization of pattern formation in symmetric diblock copolymer films. J Polym Sci Part B Polym Phys 39: 2141–2158
Webster DC (2008) Combinatorial and high-throughput methods in macromolecular materials research and development. Macromol Chem Phys 209:237–246
Green JJ, Langer R, Anderson DG (2008) A combinatorial polymer library approach yields insight into nonviral gene delivery. Acc Chem Res 41:749–759
Lynn DM, Anderson DG, Putnam D et al. (2001) Accelerated discovery of synthetic transfection vectors: parallel synthesis and screening of a degradable polymer library. J Am Chem Soc 123:8155–8156
Reynolds CH (1999) Designing diverse and focused combinatorial libraries of synthetic polymers. J Comb Chem 1:297–306
Anderson DG, Peng W, Akinc A, Hossain N, Kohn A, Padera R, Langer R, Sawicki JA (2004) A polymer library approach to suicide gene therapy for cancer. Proc Nat Acad Sci USA 101:16028–16033
Szwarc M (1956) Living polymers. Nature 178:1168–1169
IUPAC (1997) Compendium of chemical terminology, (the “Gold Book”), 2nd edn. In: McNaught AD, Wilkinson A (eds) Blackwell, Oxford (XML on-line corrected version: http://goldbook.iupac.org (2006-) created by M. Nic, J. Jirat, B. Kosata; updates compiled by A. Jenkins. ISBN 0–9678550–9–8)
Moad G, Solomon DH (1995) The chemistry of free radical polymerization. Elsevier Science, Bath
Sawamoto M, Kamigaito M (1999) In: Schlueter D (ed) Synthesis of polymers. VCH, Weinheim
Otsu T, Matsumoto A (1998) Controlled synthesis of polymers using the iniferter technique: developments in living radical polymerization. Adv Polym Sci 136:75–137
Ajayaghosh A, Francis R (1998) Narrow polydispersed reactive polymers by a photoinitiated free radical polymerization approach. Controlled polymerization of methyl methacrylate. Macromolecules 31:1436–1438
Ajayaghosh A, Francis R (1999) A xanthate-derived photoinitiator that recognizes and controls the free radical polymerization pathways of methyl methacrylate and styrene. J Am Chem Soc 121:6599–6606
Borsig E, Lazar M, Capla M (1967) Polymerization of methyl methacrylate initiated by 3,3,4,4-tetraphenyl hexane and 1,1,2,2-tetraphenyl cyclopentane. Makromol Chem 105:212
Sebenik A (1998) Living free-radical block copolymerization using thio-iniferters. Prog Polym Sci 23:875–917
Qin SH, Qiu KY, Swift G et al. (1999) “Living” radical polymerization of methyl methacrylate with diethyl 2,3-dicyano-2,3-diphenylsuccinate as a thermal iniferter. J Polym Sci Part A Polym Chem 37:4610–4615
Moad G, Rizzardo E (1995) Alkoxyamine-initiated living radical polymerization: factors affecting alkoxyamine homolysis rates. Macromolecules 28:8772–8728
Moad G, Rizzardo E, Thang SH (2008) Toward living radical polymerization. Acc Chem Res 41:1133–1142
Wang JS, Matyjaszewski K (1995) Controlled living radical polymerization – atom transfer radical polymerization in the presence of transition metal complexes. J Am Chem Soc 117:5614–5615
Kato M, Kamigaito M, Sawamoto M et al. (1995) Polymerization of methyl methacrylate with the carbon-tetrachloride dichlorotris(triphenylphosphine)-ruthenium(II) methylaluminum bis(2,6-di-tert-butylphenoxide) initiating system – possibility of living radical polymerization. Macromolecules 28:1721–1723
Kwak Y, Matyjaszewski K (2008) Effect of initiator and ligand structures on ATRP of styrene and methyl methacrylate initiated by alkyl dithiocarbamate. Macromolecules 41:6627–6635
Tang W, Matyjaszewski K (2007) Effects of initiator structure on activation rate constants in ATRP. Macromolecules 40:1858–1863
Tang W, Kwak Y, Braunecker W et al. (2008) Understanding atom transfer radical polymerization: effect of ligand and initiator structures on the equilibrium constants. J Am Chem Soc 130:10702–10713
Becer CR, Groth AM, Paulus RM et al. (2008) Protocol for automated kinetic investigation/optimization of the RAFT polymerization of various monomers. QSAR Comb Sci 27:977–983
Zhang HQ, Marin V, Fijten MWM et al. (2004) High-throughput experimentation in ATRP: a general approach toward a directed design and understanding of optimal catalytic systems. J Polym Sci Part A Polym Chem 42:1876–1885
Meier MAR, Schubert US (2006) Selected successful approaches in combinatorial materials research. Soft Matter 2:371–376
Meier MAR, Hoogenboom R, Schubert US (2004) Combinatorial methods, automated synthesis and high-throughput screening in polymer research: the evolution continues. Macromol Rapid Commun 25:21–33
Hoogenboom R, Meier MAR, Schubert US (2003) Combinatorial methods, automated synthesis and high-throughput screening in polymer research: past and present. Macromol Rapid Commun 24:15–32
Meier MAR, Schubert US (2004) Combinatorial polymer research and high-throughput experimentation: powerful tools for the discovery and evaluation of new materials. J Mater Chem 14:3289–3299
Zhang HQ, Hoogenboom R, Meier MAR et al. (2005) Combinatorial and high-throughput approaches in polymer science. Meas Sci Technol 16:203–211
Guerrero-Sanchez G, Paulus RM, Fijten MWM et al. (2006) High-throughput experimentation in synthetic polymer chemistry: from RAFT and anionic polymerizations to process development. Appl Surf Sci 252:2555–2561
Zhang HQ, Abeln CH, Fijten MWM et al. (2006) High-throughput experimentation applied to atom transfer radical polymerization: automated optimization of the copper catalysts removal from polymers. e-polymers 8:1–9
Zhang HQ, Fijten MWM, Hoogenboom R et al. (2003) Application of a parallel synthetic approach in atom transfer radical polymerization: set up and feasibility demonstration. Macromol Rapid Commun 24:81–86
Moad G, Rizzardo E, Solomon DH (1982) Selectivity of the reaction of free radicals with styrene. Macromolecules 15:909–914
Georges MK, Veregin RPN, Kazmaier PM et al. (1993) Narrow molecular weight resins by a free radical polymerization process. Macromolecules 26:2987–2988
Hawker CJ (1994) Molecular weight control by a living free radical process. J Am Chem Soc 116:11185–11186
Hawker CJ, Barclay GG, Orellana A et al. (1996) Initiating systems for nitroxide-mediated “living” free radical polymerizations: synthesis and evaluation. Macromolecules 29:5245–5254
Benoit D, Grimaldi S, Robin S et al. (2000) Kinetics and mechanism of controlled free-radical polymerization of styrene and n-butyl acrylate in the presence of an acyclic beta-phosphonylated nitroxide. J Am Chem Soc 122:5929–5939
Benoit D, Chaplinski V, Braslau R et al. (1999) Development of a universal alkoxyamine for “living” free radical polymerizations. J Am Chem Soc 121:3904–3920
Becer CR, Paulus RM, Hoogenboom R et al. (2006) Optimization of the NMRP conditions for styrene and tert-butylacrylate in an automated parallel synthesizer. J Polym Sci Part A Polym Chem 44:6202–6213
Eggenhuisen TM, Becer CR, Fijten MWM et al. (2008) Libraries of statistical hydroxypropyl acrylate containing copolymers with LCST properties prepared by NMP. Macromolecules 41:5132–5140
Chiefari J, Chong YK, Ercole F (1998) Living free radical polymerization by reversible addition-fragmentation chain transfer – the RAFT process. Macromolecules 31:5559–5562
Corpart P, Charmot D, Biadatti T et al. (1999) Block polymer synthesis by controlled radical polymerization. (WO9858974) Chem Abstr 130:82018
Chapon P, Mignaud C, Lizarraga G et al. (2003) Automated parallel synthesis of MADIX (co)polymers. Macromol Rapid Commun 24:87–91
Fijten MWM, Paulus RM, Schubert US (2005) Systematic parallel investigation of RAFT polymerizations for eight different (meth)acrylates: a basis for the designed synthesis of block and random copolymers. J Polym Sci Part A Polym Chem 43:3831–3839
Guerrero-Sanchez C, Abeln C, Schubert US (2005) Automated parallel anionic polymerizations: enhancing the possibilities of a widely used technique in polymer synthesis. J Polym Sci Part A Polym Chem 43:4151–4160
Gilman H, Jaubein AH (1941) The quantitative analysis of alkyllithium compounds. J Am Chem Soc 66:1515–1516
Hadjichristidis N, Iatrou H, Pispas S et al. (2000) Anionic polymerization: high vacuum techniques. J Polym Sci Part A Polym Chem 38:3211–3234
Glusker DL, Lysloff I, Stiles E (1961) Mechanism of anionic polymerization of methyl methacrylate II. Use of molecular weight distributions to establish a mechanism. J Polym Sci 49:315–334
Auguste S, Edwards HGM, Johnson AF et al. (1996) Anionic polymerization of styrene and butadiene initiated by n-butyllithium in ethylbenzene: determination of the propagation rate constants using Raman spectroscopy and gel permeation chromatography. Polymer 37:3665–3673
Wang GM, van Beylen M (2003) Influence of π-complexing agents on the anionic polymerization of styrene with lithium as counterion in cyclohexane. 1. Effect of durene. Polymer 44:6205–6210
Tomalia DA, Sheetz DP (1966) Homopolymerization of 2-alkyl and 2-aryl-2-oxazolines. J Polym Sci Part A Polym Chem 4:2253–2265
Seelinger W, Aufderhaar E, Diepers W et al. (1966) Recent synthesis and reactions of cyclic imidic esters. Angew Chem 20:913–927
Hoogenboom R, Fijten MWM, Paulus RM et al. (2006) Accelerated pressure synthesis and characterization of 2-oxazoline block copolymers. Polymer 47:75–84
Hoogenboom R, Fijten MWM, Schubert US (2004) The effect of temperature on the living cationic polymerization of 2-phenyl-2-oxazoline explored utilizing an automated synthesizer. Macromol Rapid Commun 25:339–343
Hoogenboom R, Fijten MWM, Schubert US (2004) Parallel kinetic investigation of 2-oxazoline polymerizations with different initiators as basis for designed copolymer synthesis. J Polym Sci Part A Polym Chem 42:1830–1840
Hoogenboom R, Wiesbrock F, Leenen MAM et al. (2005) Accelerating the living polymerization of 2-nonyl-2-oxazoline by implementing a microwave synthesizer into a high-throughput experimentation workflow. J Comb Chem 7:10–13
Hoogenboom R, Paulus RM, Fijten MWM et al. (2005) Concentration effects in the CROP of 2-ethyl-2-oxazoline in N,N-dimethyl acetamide. J Polym Sci Part A Polym Chem 43: 1487–1497
Wiesbrock F, Hoogenboom R, Leenen MAM et al. (2005) Investigation of the living cationic ring-opening polymerization of 2-methyl, 2-ethyl, 2-nonyl, and 2-phenyl-2-oxazoline in a single-mode microwave reactor. Macromolecules 38:5025–5034
Paulus RM, Becer CR, Hoogenboom R et al. (2008) Acetyl halide initiator screening for the cationic ring opening polymerization of 2-ethyl-2-oxazoline. Macromol Chem Phys 209: 794–800
Yagci Y, Tasdelen MA (2006) Mechanistic transformations involving living and controlled/living polymerization methods. Prog Polym Sci 31:1133–1170
Bernaerts KV, Du Prez FE (2006) Dual/heterofunctional initiators for the combination of mechanistically distinct polymerization techniques. Prog Polym Sci 31:671–722
Becer CR, Paulus RM, Hoppener S et al. (2008) Synthesis of poly(2-ethyl-2-oxazoline)-b-poly(styrene) copolymers via a dual initiator route combining cationic ring opening polymerization and atom transfer radical polymerization. Macromolecules 41:5210–5215
Becer CR, Hahn S, Fijten MWM et al. (2008) Libraries of MAA and OEGMA copolymers with LCST behavior. J Polym Sci Part A Polym Chem 46:7138–7147
Fournier D, Hoogenboom R, Thijs HML, Paulus RM, Schubert US (2007) Tunable pH- and temperature-sensitive copolymer libraries by RAFT of methacrylates. Macromolecules 40:915–920
Lutz JF, Hoth A (2006) Preparation of ideal PEG analogues with a tunable thermosensitivity by controlled radical copolymerization of 2-(2-methoxyethoxy)ethyl methacrylate and oligo(ethylene glycol) methacrylate. Macromolecules 39:893–896
Lutz JF (2008) Polymerization of oligo(ethylene glycol) (meth)acrylates: toward new generations of smart biocompatible materials. J Polym Sci Part A Polym Chem 46:3459–3470
Thomas EL, Anderson DM, Henkee CS et al. (1988) Periodic area-minimizing surfaces in block copolymers. Nature 334:598–601
Lohmeijer BGG, Wouters D, Yin ZH et al. (2004) Block copolymer libraries: modular versatility of the macromolecular Lego (R) system. Chem Commun 24:2886–2887
Pochan DJ, Chen Z, Cui H et al. (2004) Toroidal triblock copolymer assemblies. Science 306:94–97
Jain S, Bates FS (2003) On the origins of morphological complexity in block copolymer surfactants. Science 300:460–464
Gohy JF (2005) Block copolymer micelles. Adv Polym Sci 190:65–136
Ladaviere C, Dorr N, Claverie JP (2001) Controlled radical polymerization of acrylic acid in protic media. Macromolecules 34:5370–5372
Couvreur L, Lefay C, Belleney J (2003) First nitroxide-mediated controlled free-radical polymerization of acrylic acid. Macromolecules 36:8260–8267
Haddleton DM, Crossman MC, Dana BH et al. (1999) Atom transfer polymerization of methyl methacrylate mediated by alkylpyridylmethan-imine type ligands, copper(I) bromide, and alkyl halides in hydrocarbon solution. Macromolecules 32:2110–2119
Butun V, Vamvakaki M, Billingham NC et al. (2000) Synthesis and aqueous solution properties of novel neutral/acidic block copolymers. Polymer 41:3173–3182
Mori H, Muller AHE (2003) New polymeric architectures with (meth)acrylic acid segments. Prog Polym Sci 28:1403–1439
Hoogenboom R, Schubert US, van Camp W et al. (2005) RAFT polymerization of 1-ethoxy ethyl acrylate: a novel route toward near-monodisperse poly(acrylic acid) and derived block copolymer structures. Macromolecules 38:7653–7659
Hoogenboom R, Fijten MWM, Wijnans S et al. (2006) High-throughput synthesis and screening of a library of random and gradient copoly(2-oxazoline)s. J Comb Chem 8:145–148
Hoogenboom R, Fijten MWM, Thijs HML et al. (2007) Synthesis, characterization, and cross-linking of a library of statistical copolymers based on 2-“soy alkyl”-2-oxazoline and 2-ethyl-2-oxazoline. J Polym Sci Part:A Polym Chem 45:5371–5379
Wiesbrock F, Hoogenboom R, Leenen M et al. (2005) Microwave-assisted synthesis of a 4 ×2-membered library of diblock copoly(2-oxazoline)s and chain-extended homo poly(2-oxazoline)s and their thermal characterization. Macromolecules 38:7957–7966
Hoogenboom R, Wiesbrock F, Huang H et al. (2006) Microwave-assisted cationic ring-opening polymerization of 2-oxazolines: a powerful method for the synthesis of amphiphilic triblock copolymers. Macromolecules 39:4719–4725
Lohmeijer BGG, Schubert US (2002) Supramolecular engineering with macromolecules: an alternative concept for block copolymers. Angew Chem Int Ed 41:3825–3829
Lohmeijer BGG, Schubert US (2005) The LEGO toolbox: supramolecular building blocks by NMP. J Polym Sci Part A Polym Chem 43:6331–6344
Lohmeijer BGG, Schubert US (2003) Water-soluble building blocks for metallo-supramolecular polymers: synthesis, complexation and decomplexation studies of poly(ethyleneoxide) moities. Macromol Chem Phys 204:1072–1078
Gohy JF, Lohmeijer BGG, Schubert US (2003) From supramolecular block copolymers to advanced nano-objects. Chem Eur J 9:3472–3479
Meier MAR, Lohmeijer BGG, Schubert US (2003) Characterization of defined metal containing supramolecular block copolymers. Macromol Rapid Commun 24:852–857
Lohmeijer BGG, Schubert US (2004) Expanding the supramolecular polymer LEGO system: nitroxide mediated living free radical polymerization for metallo-supramolecular block copolymers with a polystyrene block. J Polym Sci Part A Polym Chem 42:4016–4027
Gohy JF, Lohmeijer BGG, Alexeev A, Wang XS, Manners I, Winnik MA, Schubert US (2004) Cylindrical micelles from the aqueous self-assembly of an amphiphilic poly(ethylene oxide)-b-poly(ferrocenylsilane) (PEO-b-PFS) block copolymer with a metallo-supramolecular linker at the block junction. Chem Eur J 20:4315–4323
Hofmeier H, El-ghayoury A, Schenning APH, Schubert US (2004) New supramolecular polymers containing both terpyridine metal complexes and quadruple hydrogen bonding units. Chem Commun 318–319
Zhu L, Chen Y, Zhang AQ et al. (1999) Phase structures and morphologies determined by competitions among self-organization, crystallization, and vitrification in a disordered poly(ethylene oxide)-b-polystyrene diblock copolymer. Phys Rev B Condens Matter 60:10022–10031
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Financial support from the Dutch Polymer Institute (DPI project #502) is gratefully acknowledged.
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Becer, C.R., Schubert, U.S. (2010). Parallel Optimization and High-Throughput Preparation of Well-Defined Copolymer Libraries Using Controlled/“Living” Polymerization Methods. In: Meier, M., Webster, D. (eds) Polymer Libraries. Advances in Polymer Science, vol 225. Springer, Berlin, Heidelberg. https://doi.org/10.1007/12_2009_16
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