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Title: Well-defined polymeric architectures by reversible addition-fragmentation chain transfer polymerisation : synthesis, characterisation and application as oil and lubricant additives
Author: Moriceau, Guillaume
ISNI:       0000 0004 7961 1559
Awarding Body: University of Warwick
Current Institution: University of Warwick
Date of Award: 2018
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Reversible addition-fragmentation chain transfer (RAFT) polymerisation was exploited to synthesise well-defined graft copolymers via a scalable route and study their potential as oil and lubricant additives (rheology modifiers). The RAFT polymerisation process was adapted to industrial conditions (industrial grade CTA and one-pot process) and graft materials were synthesised using styrene and maleic anhydride as a comonomer system (polystyrene-co-maleic anhydride or PSMA). Prior to synthesising well-defined materials, the purity of the industrial grade CTA-Ester from Lubrizol (c.a. 80 %) and its performances (Ctr and kinetics) for styrene and methacrylates (methyl and lauryl) monomers were determined. RAFT polymerisation conditions were optimised and a polystyrene macroCTA (DP = 10) with controlled molar mass, narrow dispersity and high livingness was obtained. A one-pot sequential monomer addition strategy was developed to synthesise a multisite copolymer composed of a polystyrene backbone (DP = 50) with maleic anhydride units inserted locally (every 10 units in average). The subsequent functionalisation of maleic anhydride moieties with long aliphatic alcohols (stearyl/C18) yield to a graft material with low density of alkyl side chains. A library of well-defined PSMA materials with various composition (alternating, block, multiblock, and multisite) and topology (linear, star, and graft) was also achieved. The subsequent functionalisation of the PSMA copolymers with various aliphatic alcohols (lauryl/C12 and behenyl/C22) allowed the preparation of graft materials with controlled density and distribution of side chains. The influence of copolymer composition and structure, and the effect of long alkyl chain addition on the physical and thermal properties of the materials, were demonstrated. Finally, the well-defined graft PSMA materials were investigated as rheology modifiers in two mineral oils (group II and III) and the influence of polymer composition, grafting density and distribution, molar mass, and side chain length on pour point, viscosity index (VI) and thickening efficiency (TE) were investigated. The performances of graft PSMA materials as oil and lubricant additives were demonstrated.
Supervisor: Not available Sponsor: Lubrizol Corporation
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: QD Chemistry