Prof. Lian Hutchings
(email at email@example.com)
Deputy Director of the Durham Centre for Soft Matter
My interests lie in the field of synthetic polymer chemistry and specifically the synthesis of polymers which are well controlled in terms of molecular weight, composition, functionality and chain architecture. We also collaborate extensively in studies which seek to understand the correlation between structure and properties. We exploit a variety of living/controlled polymerization mechanisms to achieve that aim including living anionic polymerization, ATRP and RAFT
DendriMacs, HyperMacs and HyperBlocks1,2
It is well understood that the architecture of polymer molecules, particularly branching has a strong influence on the physical properties. Experimental tests of current theories for the correlation of molecular architecture and physical properties require model polymers with precisely defined structures. As the theoreticians develop increasingly sophisticated tools the challenge for the synthetic polymer chemist is to create evermore complex yet well defined branched architectures.
In recent years we have developed a very versatile methodology to synthesise a new generation of long chain branched polymers we call DendriMacs and HyperMacs1. These architectures are essentially long chain branched analogues of dendrimers and hyperbranched polymers - analogous not only in structure but in the strategy used to prepare them. They differ from dendrimers and hyperbranched polymers only in having a well defined polymer chain between branch points. They have been used as the ultimate long chain branched polymer for structure property correlation studies; leading to validation of the most advanced theoretical tools for the prediction of the rheology of branched polymers. More recently block copolymeric HyperMacs - HyperBlocks have shown promise as a novel branched thermoplastic elastomers2.
Polymers containing functionality at one (or both ends) of the polymer chain can, when used in relatively small quantities, significantly modify interfaces, be it a polymer/air interface, air/liquid interface or if the functionalities are reactive, functionalized polymers can be used to stabilize a polymer blend, via reactive blending. We have an ongoing collaborative research program (with Dr Richard Thompson) investigating the surface modifying properties of multi end functionalized polymer additives for a variety of applications. Multi functional fluoroalkyl additives have been shown to be particularly effective at rendering the surface of the polymers extremely hydrophobic with less than 0.5% of additive required to modify the surface of a polystyrene film to give PTFE like surface properties. See below the relationship between contact angle (with water) and the concentration of polymer additive.
Control of sequence distribution in copolymers6
The control of sequence distribution in polymers is something that nature achieves with consummate ease with sequence-defined polymers such as nucleic acids and proteins being the fundamental building blocks of life. However the ability to reproduce this level of control in synthetic polymer chemistry is a highly challenging and often neglected area of research, despite the possibility that synthetic polymers with controlled monomer sequences could play a significant role in the future of materials science. Some progress has been made for step wise condensation polymerisation using protection/deprotection reaction cycles on solid supports but the control of sequence for chain growth polymerisation in solution is an altogether more challenging problem. Possibly the simplest form of sequence control in chain growth polymerisation is the alternating copolymer and we have recently begun to investigate new combinations of monomers capable of generating alternating sequences. Our longer term goal is to create polymers from 3 or 4 comonomers which as a result of inherent differences in reactivity polymerise in a strictly controlled sequence.
- Hutchings, LR; Dodds, JM; Rees, D; Kimani, SM; Wu, JJ; Smith, E. HyperMacs to HyperBlocks: A Novel Class of Branched Thermoplastic Elastomer. Macromolecules, 2009, 42, 8675-8687
- Hutchings, LR. DendriMacs and HyperMacs. Emerging as more than just model branched polymers. Soft Matter. 2008, 4, 2150-2159
- Hutchings, LR; Sarih, NM; Thompson, RL. Multi-end functionalised polymer additives synthesised by living anionic polymerisation - the impact of additive molecular structure upon surface properties. Polymer Chemistry, 2011, 2, 851-861
- Pillay Narrainen, A; Hutchings, LR; Ansari, I; Thompson, RL; Clarke, N. Modifying and Managing the Surface Properties of Polymers - A Mini Reveiw. Polymer International, 2008, 57, 163-170.
- Pillay Narrainen, A; Hutchings, LR; Ansari, I; Thompson, RL; Clarke, N. Multi-end functionalized polymers; additives to modify polymer properties at surfaces and interfaces. Macromolecules, 2007, 40, 1969-1980.
- Natalello, A; Hall, JN; Eccles, EAL; Kimani, SM; Hutchings, LR. Kinetic Control of Monomer Sequence Distribution in Living Anionic Copolymerisation. Macromoecular Rapid Communications, 2011, 32, 233-237.
Department of Chemistry
- Soft Matter and Interfaces
- Synthetic Polymer Chemistry
- Branched Polymers
- Functional Polymers
Chapter in book
- Khosravi, E, Castle, TC, Kujawa, M, Leejarkpai, J, Hutchings, LR & Hine, PJ (2009). Chapter Chapter 14. In New Smart Materials via Metal Mediated Macromolecular Engineering. Khosravi, E, Yagci, Y & Savelyev, Y Springer. 223-236.
- Shaw, Lloyd & Hutchings, Lian R. (2020). Tales of the unexpected. The non-random statistical copolymerisation of myrcene and styrene in the presence of a polar modifier’. Polymer Chemistry
- Hutchings, Lian R., Brooks, Paul P., Shaw, Peter & Ross-Gardner, Paul (2019). Fire and Forget! One-Shot Synthesis and Characterization of Block-Like Statistical Terpolymers via Living Anionic Polymerization. Journal of Polymer Science Part A: Polymer Chemistry 57(3): 382-394.
- Yolsal, Utku & Hutchings, Lian R. (2019). Synthesis and Coupling of ABx Polysiloxane Macromonomers to Form Highly Branched Polysiloxanes. European Polymer Journal 113: 254-259.
- Grune, Eduard, Bareuther, Jennifer, Blankenburg, Jan, Appold, Michael, Shaw, Lloyd, Mueller, Axel H. E., Floudas, George, Hutchings, Lian R., Gallei, Markus & Frey, Holger (2019). Towards bio-based tapered block copolymers: the behaviour of myrcene in the statistical anionic copolymerisation. Polymer Chemistry
- Boulding, Natasha A., Millican, Jonathan M. & Hutchings, Lian R. (2019). Understanding copolymerisation kinetics for the design of functional copolymers via free radical polymerisation. Polymer Chemistry 10(41): 5665-5675.
- Pagliarulo, Antonella & Hutchings, Lian R. (2018). End-Functionalized Chains via Anionic Polymerization: Can the Problems with Using Diphenylethylene Derivatives be Solved by using Bisphenol F? Macromolecular Chemistry and Physics 219(1): 1700386.
- Sánchez-Valencia, Andrea, Smerdova, Olga, Hutchings, Lian R. & De Focatiis, Davide S. A. (2017). The Roles of Blending and of Molecular Weight Distribution on Craze Initiation. Macromolecules 50(23): 9507-9514.
- Rowan, Stuart J., Barner-Kowollik, Christopher, Klumperman, Bert, Gaspard, Pierre, Grubbs, Robert B., Hillmyer, Marc A., Hutchings, Lian R., Mahanthappa, Mahesh K., O'Reilly, Rachel K. Ouchi, Makoto, Sawamoto, Mitsuo & Lodge, Timothy P. (2016). Discussion on “Aperiodic Copolymers”. ACS Macro Letters 5(1): 1-3.
- Huang, Qian, Agostini, Serena, Hengeller, Ludovica, Shivokhin, Maksim, Alvarez, Nicolas J., Hutchings, Lian R. & Hassager, Ole (2016). Dynamics of Star Polymers in Fast Extensional Flow and Stress Relaxation. Macromolecules 49(17): 6694-6699.
- Hutchings, Lian R., Agostini, Serena, Hamley, Ian W. & Hermida-Merino, Daniel (2015). Chain Architecture as an Orthogonal Parameter To Influence Block Copolymer Morphology. Synthesis and Characterization of Hyperbranched Block Copolymers: HyperBlocks. Macromolecules 48(24): 8806-8822.
- Hutchings, Lian R., Brooks, Paul P., Parker, David, Mosely, Jackie A. & Sevinc, Serkan (2015). Monomer Sequence Control via Living Anionic Copolymerization: Synthesis of Alternating, Statistical, and Telechelic Copolymers and Sequence Analysis by MALDI ToF Mass Spectrometry. Macromolecules 48(3): 610-628.
- Hutchings, Lian R., Agostini, S., Oti, Matthew E. & Keth, Jennifer (2015). Normal-phase (temperature gradient) interaction chromatography – A powerful tool for the characterisation of high molecular weight chain-end functionalised polymers. European Polymer Journal 73: 105-115.
- Smerdova, O., Graham, R.S., Gasser, U., Hutchings, L.R. & De Focatiis, D.S.A. (2014). A Novel Method of Extraction of Blend Component Structure from SANS Measurements of Homopolymer Bimodal Blends. Macromolecular Chemistry and Physics 215(9): 859-866.
- Kimani, S.M., Thompson, R.L., Hutchings, L.R., Clarke, N., Billah, S.M.R., Sakai, V.G. & Rogers, S.E. (2014). Multihydroxyl End Functional Polyethylenes: Synthesis, Bulk and Interfacial Properties of Polymer Surfactants. Macromolecules 47(6): 2062-2071.
- Bergius, W.N.A., Hutchings, L.R., Sarih, N.M., Thompson, R.L., Jeschke, M. & Fisher, R. (2013). Synthesis and characterisation of end-functionalised poly(N-vinylpyrrolidone) additives by reversible addition–fragmentation transfer polymerisation. Polymer Chemistry 4(9): 2815-2827.
- Agostini, Serena & Hutchings, Lian R. (2013). Synthesis and temperature gradient interaction chromatography of model asymmetric star polymers by the "macromonomer" approach. European Polymer Journal 49(9): 2769-2784.
- Hutchings LR (2012). Complex Branched Polymers for Structure-Property Correlation Studies: The Case for Temperature Gradient Interaction Chromatography Analysis. Macromolecules 45(14): 5621-5639.
- Hutchings, Lian R., Kimani, Solomon M., Hoyle, David M., Read, Daniel J., Das, Chinmay, McLeish, Thomas C. B., Chang, Taihyun, Lee, Hyojoon & Auhl, Dietmar (2012). In Silico Molecular Design, Synthesis, Characterization, and Rheology of Dendritically Branched Polymers: Closing the Design Loop. ACS macro letters 1(3): 404-408.
- Hardman, S.J., Hutchings, L.R., Clarke, N., Kimani, S.M., Mears, L.L.E., Smith, E.F., Webster, J.R.P. & Thompson, R.L. (2012). Surface Modification of Polyethylene with Multi-End-Functional Polyethylene Additives. Langmuir 28(11): 5125-5137.
- Kimani, SM, Hardman, SJ, Hutchings, LR, Clarke, N & Thompson, RL (2012). Synthesis and surface activity of high and low surface energy multi-end functional polybutadiene additives. Soft Matter 8(12): 3487-3496.
- Hardman, S.J., Muhamad-Sarih, N., Riggs, H.J., Thompson, R.L., Rigby, J., Bergius, W.NA. & Hutchings, L.R. (2011). Electrospinning Superhydrophobic Fibers Using Surface Segregating End-Functionalized Polymer Additives. Macromolecules 44(16): 6461-6470.
- Hutchings, L.R., Sarih, N.M. & Thompson, R.L. (2011). Multi-end functionalised polymer additives synthesised by living anionic polymerisation-the impact of additive molecular structure upon surface properties. Polymer Chemistry 2(4): 851-861.
- Sedransk, KL, Kaminski, CF, Hutchings, LR & Moggridge, GD (2011). The metathetic degradation of polyisoprene and polybutadiene in block copolymers using Grubbs second generation catalyst. Polymer Degradation and Stability 96(6): 1074-1080.
- Clarke, N., De Luca, E., Buxton, G., Hutchings, L.R., Gough, T., Grillo, I., Graham, R.S., Jagannathan, K., Klein, D.H. & McLeish, T.C.B. (2010). Chain Deformation in Entangled Polymer Melts at Re-entrant Corners. Macromolecules 43(3): 1539-1542.
- Dodds, JM & Hutchings, LR (2010). HyperMacs - Highly Branched Network Precursors or Semi-Interpenetrating Networks? Macromolecular Symposia 291-292(1): 26-35.
- Natalello, A, Hall, JN, Eccles, EAL, Kimani, SM & Hutchings, LR (2010). Kinetic Control of Monomer Sequence Distribution in Living Anionic Copolymerisationa. Macromolecular Rapid Communications 32(2): 233-237.
- Hutchings, LR, Douglas, CJR Rhodes, CL Carswell, WD Skoda, MWA, Webster, JRP & Thompson, RL (2010). Nonsolvent Annealing Polymer Films with Ionic Liquids. Langmuir 26(19): 15486-15493.
- Hutchings, L.R., Dodds, J.M., Rees, D., Kimani, S.M., Wu, J.J. & Smith, E. (2009). HyperMacs to HyperBlocks: A Novel Class of Branched Thermoplastic Elastomer. Macromolecules 42(22): 8675-8687.
- McLeish, Tom C.B., Clarke, Nigel, de Luca, Eduardo, Hutchings, Lian R., Graham, Richard S., Gough, Tim, Grillo, Isabelle, Fernyhough, Christine M. & Chambon, Pierre (2009). Neutron flow-mapping: Multiscale modelling opens a new experimental window. Soft Matter 5(22): 4426-4432.
- Thompson, RL , Hardman, SJ Hutchings, LR , Narrainen, AP & Dalgliesh, RM (2009). pH-Controlled Polymer Surface Segregation. Langmuir 25(5): 3184-3188.
- Clarke, N, Hutchings, LR, Robinson, I, Elder, JA & Collins, SA (2009). Suspension Polymerization of Poly(methyl methacrylate)/Clay Nanocomposites. Journal of Applied Polymer Science 113(2): 1307-1315.
- Graham, Richard S., Bent, Julian, Clarke, Nigel, Hutchings, Lian R., Richards, Randal W., Gough, Tim, Hoyle, David M., Harlen, Oliver G., Grillo, Isabelle, Auhl, Dietmar & McLeish, Tom C.B. (2009). The long-chain dynamics in a model homopolymer blend under strong flow: small-angle neutron scattering and theory. Soft Matter 5(12): 2383-2389.
- Kimani, SM & Hutchings, LR (2008). A facile route to synthesize well-defined polybutadiene DendriMacs. Macromolecular Rapid Communications 29(8): 633-637.
- Hutchings, L.R. (2008). DendriMacs and HyperMacs - emerging as more than just model branched polymers. Soft Matter 4(11): 2150-2159.
- Clarke, N., De Luca, E., Dodds, J.M., Kimani, S.M. & Hutchings, L.R. (2008). HyperMacs – long chain hyperbranched polymers: A dramatically improved synthesis and qualitative rheological analysis. European Polymer Journal 44(3): 665-676.
- De Focatiis, D.S.A., Buckley, C.P. & Hutchings, L.R. (2008). Roles of chain length, chain architecture, and time in the initiation of visible crazes in polystyrene. Macromolecules 41(12): 4484-4491.
- Hutchings, LR (2007). Modifying and managing the surface properties of polymers. Polymer International 57(2): 163-170.
- A.P. Narrainen, L.R. Hutchings, I. Ansari, R.L. Thompson & N. Clarke (2007). Multi-end-functionalized polymers: additives to modify polymer properties at surfaces and interfaces. Macromolecules 40(6): 1969-1980.
- Thompson, RL, Narrainen, AP, Eggleston, SM, Ansari, IA & Hutchings, LR (2007). Recoverable surface modification using dendritically fluorocarbon-functionalized poly(methyl methacrylate). Journal of Applied Polymer Science 105(2): 623-628.
- Dodds, JM, De Luca, E, Hutchings, LR & Clarke, N (2007). Rheological properties of HyperMacs - Long-chain branched analogues of hyperbranched polymers. Journal of Polymer Science Part B: Polymer Physics 45(19): 2762-2769.
- Castle, T.C., Khosravi, E. & Hutchings, L.R. (2006). Block copolymers by the conversion of living lithium initiated anionic polymerization into living ruthenium ROMP. Macromolecules 39(17): 5639-5645.
- Hutchings, L.R. & Roberts-Bleming, S.J. (2006). DendriMacs. Well-defined dendritically branched polymers synthesized by an iterative convergent strategy involving the coupling reaction of AB₂ macromonomers. Macromolecules 39(6): 2144-2152.
- Hutchings, L.R., Dodds, J.M. & Roberts-Bleming, S.J. (2006). HyperMacs. Long chain branched analogues of hyperbranched polymers prepared by the polycondensation of AB(2) macromonomers. Macromolecular symposia 240(1): 56-67.
- Hutchings, L.R. (2006). Macromolecular engineering: a synthetic perspective. Plastics, rubber and composites 35(10): 403-409.
- Graham, R.S., Bent, J., Hutchings, L.R., Richards, R.W., Groves, D.J., Embery, J., Nicholson, T.M., McLeish, T.C.B., Likhtman, A.E., Harlen, O.G., Read, D.J., Gough, T., Spares, R., Coates, P.D. & Grillo, I. (2006). Measuring and predicting the dynamics of linear monodisperse entangled polymers in rapid flow through an abrupt contraction. A small angle neutron scattering study. Macromolecules 39(7): 2700-2709.
- A. Pillay Narrainen, L.R. Hutchings, I. Ansari, N. Clarke & R.L. Thompson (2006). Novel multi end-functionalised polymers. Additives to modify polymer properties at surfaces and interfaces. Soft Matter 2(2): 126-128.
- N. Clarke, E. De Luca, J. Bent, G. A. Buxton, T. Gough, I. Grillo & L. R. Hutchings (2006). Polymer blends in a contraction-expansion flow. Macromolecules 39(22): 7607-7616.
- A. P. Narrainen, N. Clarke, S. M. Eggleston, L. R. Hutchings & R. L. Thompson (2006). Surface adsorption of polar end-functionalised polystyrenes. Soft Matter 2(11): 981-985.
- L. R. Hutchings, A. P. Narrainen, S. M. Eggleston, N. Clarke & R. L. Thompson (2006). Surface-active fluorocarbon end-functionalized polylactides. Polymer 47(24): 8116-8122.
- Fernyhough, C.M., Young, R.N., Ryan, A.J. & Hutchings, L.R. (2006). Synthesis and characterisation of poly(sodium 4-styrenesulfonate) combs. Polymer 47(10): 3455-3463.
- Collis, M.W., Lele, A.K., Mackley, M.R., Graham, R.S., Groves, D.J., Likhtman, A.E., Nicholson, T.M., Harlen, O.G., McLeish, T.C.B., Hutchings, L.R., Fernyhough, C.M. & Young, R.N. (2005). Constriction flows of monodisperse linear entangled polymers: Multiscale modeling and flow visualization. Journal of Rheology 49(2): 501-522.
- L. R. Hutchings, J. M. Dodds & S. J. Roberts-Bleming (2005). HyperMacs: Highly branched polymers prepared by the polycondensation of AB₂ macromonomers, synthesis and characterization. Macromolecules 38(14): 5970-5980.
- Clarke, N., Colley, F.R., Collins, S.A., Hutchings, L.R. & Thompson, R.L. (2005). Self-diffusion and viscoelastic measurements of polystyrene star polymers. Macromolecules 39(3): 1290-1296.
- R. L. Thompson, M. T. McDonald, J. T. Lenthall & L. R. Hutchings (2005). Solvent accelerated polymer diffusion in thin films. Macromolecules 38(10): 4339-4344.
- T. C. Castle, E. Khosravi & L. R. Hutchings (2004). Block copolymers by the conversion of living lithium anionic polymerization into living ruthenium ROMP. Abstracts of Papers of the American Chemical Society 228: U328-U328.
- T. C. Castle, L. R. Hutchings & E. Khosravi (2004). Synthesis of block copolymers by changing living anionic polymerization into living ring opening metathesis polymerization. Macromolecules 37(6): 2035-2040.
- E. Khosravi, L. R. Hutchings & M. Kujawa-Welten (2004). Synthesis of well-defined graft co-polymers via coupled living anionic and living ring-opening metathesis polymerisation. Designed Monomers and Polymers 7(6): 619-632.
- M. L. Coote, D. H. Gordon, L. R. Hutchings, R. W. Richards & R. M. Dalgliesh (2003). Neutron reflectometry investigation of polymer-polymer reactions at the interface between immiscible polymers. Polymer 44(25): 7689-7700.
- Bent, J, Hutchings, LR, Richards, RW, Gough, T, Spares, R, Coates, PD, Grillo, I, Harlen, OG, Read, DJ, Graham, RS, Likhtman, AE, Groves, DJ, Nicholson, TM & McLeish, TCB (2003). Neutron-mapping polymer flow: Scattering, flow visualization, and molecular theory. SCIENCE 301(5640): 1691-1695.
- L. R. Hutchings, R. W. Richards, R. L. Thompson & D. G. Bucknall (2002). Film thickness effects on the distribution of high-molecular-weight heterotelechelic polymers. European Physical Journal E 8(2): 121-128.
- Milling, A. J., Hutchings, L. R. & Richards, R. W. (2001). Capillary wave properties of a spread film of a polybutadiene- poly(ethylene oxide) block copolymer: 1. Air-water interface. Langmuir 17(17): 5297-5304.
- Milling, A. J., Hutchings, L. R. & Richards, R. W. (2001). Capillary wave properties of a spread film of a polybutadiene- poly(ethylene oxide) block copolymer: 2. Cyclohexane-water interface. Langmuir 17(17): 5305-5313.
- J. Bowers, A. Zarbakhsh, J. R. P. Webster & L. R. HutchingsR. W. Richards (2001). Neutron reflectivity studies at liquid-liquid interfaces: Methodology and analysis. Langmuir 17(1): 140-145.
- L. R. Hutchings, R. W. Richards, R. L. Thompson & D. G. BucknallA. S. Clough (2001). Partitioning of a heterotelechelic polystyrene to separate interfaces of thin films. European Physical Journal E 5(4): 451-464.
- L. R. Hutchings, R. W. Richards & S. W. ReynoldsR. L. Thompson (2001). Small-angle neutron scattering from single arm labeled polybutadiene star polymers in dilute solution. Macromolecules 34(16): 5571-5578.
- J. Bowers, A. Zarbakhsh, J. R. P. Webster & L. R. HutchingsR. W. Richards (2001). Structure of a spread film of a polybutadiene-poly(ethylene oxide) linear diblock copolymer at the air-water interface as determined by neutron reflectometry. Langmuir 17(1): 131-139.
- A.P. Narrainen, L.R. Hutchings, W.J. Feast, R.L. Thompson, I.A. Ansari & N. Clarke (2006), Fluorocarbon end-functionalized polymers from poly(arylether) dendritic initiators, 231: 8th Conference on Macromolecules - Polymers for Africa. La Pirogue, MAURITANIA, La Pirogue, 103-109.
- L.R. Hutchings, A.P. Narrainen, N. Clarke, R.L. Thompson & I.A. Ansari (2006), Well defined multi end-functionalized polymers as additives to modify surfaces and interfaces, 231: 231st National Meeting of the American-Chemical-Society. Atlanta, GA, Atlanta GA.