Multi-Block Copolymers and Living Polymerisation

I. Altarawneh and V.G. Gomes* School of Chemical and Biomolecular Engineering, University of Sydney, NSW 2006 INTRODUCTION Block copolymers offer the potential of tuning product properties and combination of properties over a range of options. For complex, well-defined products, chemically controlled living free radical polymerisations are suitable; among them the reversible additionfragmentation chain transfer (RAFT) is the most promising [1-4]. RAFT is facilitated by compounds having structures such as Z-C(=S)S-R. During its pre-equilibrium stage, the addition of the initiator-derived propagating radical Pn* to thiocarbonylthio reagent followed by forward fragmentation of the carbon centred intermediate radical gives rise to a polymeric RAFT agent and a new reinitiating radical R*. The process is followed by forward fragmentation of carbon centred intermediate radical giving rise to a polymeric RAFT agent and a new reinitiating radical R*, which reacts with a monomer to form a new propagating radical Pm* to extend the polymeric RAFT agent. Once the RAFT agent is consumed, core equilibrium is established between the active propagating radicals (Pn* & Pm*) and the dormant polymeric RAFT agent. EXPERIMENTAL The RAFT agent (O-ethylxanthyl ethyl propionate) was synthesized in our laboratory. Styrene and Butyl acrylate monomers, initiator (sodium persulfate), purification column, and surfactant (sodium dodecyl sulfate) were obtained from Sigma-Aldrich (USA). In the first stage, polystyrene and polybutyl acrylate homopolymers were prepared with predetermined molecular weights. Emulsion polymerization was performed in a batch reactor (at 70oC) with 350 rpm agitation speed, 450g water, 3.85g AR, 1.5g SDS, 0.2g KPS, 0.08g Buffer and 150g monomer. Experiments were designed to produce polymeric latex particles containing macro-RAFT agent with a targeted molecular weight equal to 9194 g/mol at full conversion. In the second stage I (reaction 3), the entire amount of styrene (100g) was added to 260g PBA seed latexes (at 24.45% solids) from first stage (reaction 2) to produce b-PBA-co-PSt. Water (190g) and SDS (0.15g) were added to the mixture, which was then stirred overnight to swell. Emulsion polymerization of styrene in PBA seeds was started by adding 0.15g KPS under nitrogen pressure. In the second stage, styrene was polymerized in 200g PBA seeds (24.45% solids) from the first stage. The synthesis b-PSt-co-PBA under semi-batch conditions was carried out using similar procedure. Monomer conversion was determined gravimetrically, the PSD was measured using a PL-PSDA (PL-DG2), molar mass was analysed using the PL-GPC 120. A Bruker AM 400 spectroscopy (400 MHz) was used to determine the block copolymer structure and composition through 1H-NMR spectra. RESULTS AND DISCUSSIONS As butyl acrylate is invisible to UV at 254 nm, the GPC UV trace was used to verify the presence of polystyrene. Fig. 1 shows the UV-RI/Visco GPC traces for b-PBA-co-PSt (reactions 3 & 4, respectively). Both PBA homopolymers formed in the first stage have low molecular weight (i.e 9046g/mol) with low polydispersities of about 1.7, indicated by the starting GPC RI/Visco traces. The second stage batch polymerization of styrene in PBA particles produced polymers with Mn close to 23.6kg/mol with PDI equal to 2.8, respectively, as measured by GPC RI/Visco (Fig. 1a). Since BA was polymerized first (reactions 2), and followed in the second stage by styrene, a shift of UV trace towards higher molecular weight does not necessarily indicate the formation of block copolymer, as the starting PBA is invisible and cannot be detected by UV detector. However, the shift of the low molecular weight peak (RI/Visco) indicates the growth of the polymer from the original seed latex, and its transformation into a block copolymer. As shown in Fig. 1a, the UV and the RI/Visco traces largely overlap. This indicates that most of the original PBA (polybutyl acrylate) underwent addition-fragmentation chain transfer with PSt radicals to form a block copolymer (b-PBA-co-PSt) of a higher molecular weight. Fig. 1b shows the normalized UV and RI/visco chromatograms for the b-PBA-co-PSt polymer from semi-batch reaction. Here, BA was polymerized first, and styrene was polymerized in the second stage. The MWD of the starting PBA moves to higher molecular weights, displaying the living character of the original polymer. The UV-RI/Visco overlays indicate the presence of the second block (polystyrene) throughout the distribution. We observe that the low molecular weight of the RI/Visco and UV traces do not overlap. As the RI/Visco traces in Fig. 1b show the presence of low molecular weight chains with finial PDI (RI/Visco) = 2.12, we conclude that these chains are unreacted PBA polymeric RAFT agents and terminated low molecular weight PBA chains.

Analysis of the diblock copolymer (Fig. 2) demonstrates the resonances of the parent PSt (first block, Fig. 2b) by the presence of styrene aromatic protons (Phenyl group: C6H5-) at 6.25-7.22 ppm and additional resonances for PBA indicated by the resonance of OCH2 (belonging to butyl acrylate) at 4.0 ppm. Styrene and butyl acrylate mole fractions in the block copolymer (FSt, FBA, respectively) are determined from the integrals over the aromatic ring peak (Phenyl: C6H5- group), of PSt and the methylene peak (-OCH2- group) of PBA. 1H-NMR shows that the copolymer exhibits the expected composition (33.15 mol-% styrene units versus 66.15 mol-% BA units), providing evidence of block formation and the absence of homopolymer.
1.2 RI/Visco: end 1 0.8 0.6 0.4 0.2 0 1.4 1.9 2.4 2.9 3.4 3.9 4.4 4.9 5.4 5.9 UV (254nm): end RI/Visco: start

1.2 1 0.8 0.6 0.4 0.2 0 1.5 2 2.5 3 3.5 4 4.5 5 5.5
RI/Visco: start RI/Visco: end UV (254nm): end

dw/dlogM

logM

dw/dlogM

logM

Fig. 1. UV-RI/Visco overlay: (a) Batch polymerization of St in PBA, starting PDI =1.7, finial PDI (RI/Visco) = 2.8, final PDI (UV) = 2.27; (b) Semi-batch polymerization of St in PBA, starting PDI (RI/Visco) =1.7, finial PDI (RI/Visco) = 2.12, final PDI (UV) = 1.7.

Fig. 2. 1H-NMR spectrum of PSt (a); PBA (b) and b-PSt-co-PBA (c). St was polymerized first and BA was polymerized in the second stage under semi-batch conditions, sample was taken at the end of the reaction.

CONCLUSIONS Low molecular weight polymers of butyl acrylate prepared in the first stage was used as the polymeric RAFT agent to polymerize styrene in the second stage under batch and semi-batch emulsion conditions to provide well-defined block copolymers (b-PBA-co-PSt) with narrow molecular weight distributions. The process was optimized by performing semi-batch polymerization, in which the second monomer was gradually added to the reactor. This resulted in a block copolymer of high purity and relatively low polydispersity as compared with that produced under batch conditions. The choice of block sequence is important in reducing the influence of terminated chains on the distributions of polymers that were obtained. We found that polymerizing styrene first followed by the high active butyl acrylate monomer resulted in much purer block copolymer with low polydispersity as indicated by SEC and 1H-NMR measurements. REFERENCES 1. Altarawneh, I.S., V.G. Gomes and M.S. Srour, (2008). Macromol Reaction Eng, 2(1): 58-79. 2. Charmot, D. et al., (2000). Macromolecular Symposia, 150(Polymers in Dispersed Media): 23-32. 3. Chiefari, J. et al., (1998). Macromolecules, 31(16): 5559-5562. 4. Monteiro, M.J. and J. De Barbeyrac, (2001). Macromolecules, 34(13): 4416-4423.