Chung, JJ

Georgiou, T

Jones, JR

Macromolecular Rapid Communications

English

In this study the Group Transfer Polymerization (GTP) of the functional monomer 3-(trimethoxylsilyl)propyl methacrylate (TMSPMA) is reported to produce polymers of different architectures and topologies. TMSPMA was successfully polymerized and copolymerized with GTP to produce well-defined (co)polymers that can be used to fabricate functional hybrid materials like hydrogels and films

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CommunicationMacromolecularRapid Communicationswileyonlinelibrary.com1806 © 2015  The Authors. Published by WILEY-VCH Verlag GmbH &  Co.  KGaA, Weinheim DOI:  10.1002/marc.201500356 Particularly in 2004, a systematic study of TMSPMA polymerization with atom transfer radical poly-merization (ATRP) was reported. Interestingly, it was observed that when a poly(ethylene oxide) macroinitiator was used, instead of the ethyl 2-bromoisobutyrate ini-tiator, polymers with narrower  D s ranging from 1.10 to 1.39 were produced. [ 6 ] Consequently, several PEO- b -TM-SPMA diblocks were reported with ATRP with similar  D s [ 7–10 ] as well as a stearyl methacrylate TMSPMA diblock copolymer with a  M w / M n = 1.14. [ 11 ] In 2008, TMSPMA was polymerized using 1,2-bis(bromoisobutyryloxy)ethane as an initiator and a homopolymer with a  M w / M n = 1.13 was produced, which was then used as a precursor for the for-mation of an ABA triblock with a  M w / M n = 1.34. [ 12 ] Later on, more triblock [ 13,14 ] as well as pentablock [ 15,16 ] copoly-mers containing TMSPMA were synthesized by ATRP with  D s ranging from 1.16 to 1.46.  Reversible Addition-Fragmentation chain-Transfer (RAFT) polymerization has also been used to produce TMSPMA-based polymers with relatively broad  D s ranging from 1.22 to 1.49. [ 17–19 ] Only one study reported such polymers with narrow  D s (1.06 and 1.15) but the blocks consisted of no more than seven repeating units of TMSPMA. [ 20 ]  It should be noted that all the studies, where block copolymers were fabricated, used multipot and time-consuming procedures. In this study we report the  In this study, the group transfer polymerization (GTP) of the func-tional monomer 3-(trimethoxysilyl)propyl methacrylate (TMSPMA) is reported to produce polymers of different architectures and topologies. TMSPMA is successfully polymerized and copoly-merized with GTP to produce well-defi ned (co)polymers that can be used to fabricate functional hybrid materials like hydrogels and fi lms.  Toward Hybrid Materials: Group Transfer Polymerization of 3-(Trimethoxysilyl)propyl Methacrylate  Justin J.  Chung ,  Julian R.  Jones ,  Theoni K.  Georgiou *  J. J. Chung, Prof. J. R. Jones, Dr. T. K. Georgiou  Department of MaterialsRoyal School of Mines  Exhibition Road, Imperial College London  SW7 2AZ ,  London ,  UK E-mail:  t.georgiou@imperial.ac.uk  1.  Introduction  The polymerization of alkoxysilane-based monomers leads to the production of functional polymers that can later be used to produce advanced materials such as hybrid hydro-gels, fi lms, and particles. [ 1–4 ] Thus, it is not surprising that, in the last two decades with the development of controlled free-radical polymerization methods several studies report the polymerization of alkoxysilane-based monomers like 3-(trimethoxysilyl)propyl methacrylate (TMSPMA). How-ever, the fi rst report on TMSPMA polymerization was with living anionic polymerization where a polymer of 8.2 kg mol −1 and a molecular weight dispersity ( D ),  M w / M n = 1.05 was reported. [ 5 ] Since then no other study has been able to produce a TMSPMA-based homo- or copolymer of such narrow polydispersity. Macromol. Rapid Commun. 2015, 36, 1806−1809This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.MacromolecularRapid CommunicationsToward Hybrid Materials: Group Transfer Polymerization of 3-(Trimethoxysilyl)propyl Methacrylatewww.mrc-journal.de www.MaterialsViews.com 1807© 2015  The Authors. Published by WILEY-VCH Verlag GmbH &  Co.  KGaA, Weinheimone-pot synthesis of diblock copolymers. Specifi cally TMSPMA was homo- and copolymerized by group transfer polymerization (GTP), [ 21–24 ] a living polymerization method to produce linear and star (co)polymers. GTP is performed at room temperature which is a major, cost-effective, advantage compared to conventional living ani-onic polymerization where methacrylate monomers have to be polymerized at −78 °C. [ 5,22,25 ] In addition, compared to RAFT and ATRP, GTP produces polymers with narrower  D s [ 24 ] and is a much faster polymerization method. The possibility of TMSPMA being polymerized with GTP was fi rst demonstrated in 2005, [ 26 ] however the copolymers had broad  D s (1.15 to 1.5) from the TMSPMA crosslinking with the amino containing groups during the poly-merization. Here, we report the fi rst systematic study of polymerizing TMSPMA by GTP to demonstrate that well-defi ned copolymers with narrow  D s of different architec-tures and topologies can be produced. A monofunctional 1-methoxy-1(trimethylsiloxy)-2-methyl propene initiator was used for all the polymerizations.  2.  Results and Discussion  A TMSPMA homopolymer was fi rst produced to con-fi rm that it can be successfully polymerized with GTP to produce well-defi ned polymers. As can be observed in Figure  1 , unlike any controlled free-radical polymerization techniques, TMSPMA homopolymerization of 10 kg mol −1 with a  D = 1.06 took less than 15 min using GTP. In addi-tion, the TMSPMA GTP kinetics was similar to that of the most commonly used methacrylate monomer, methyl methacrylate (MMA). [ 27 ]  In order to prove that TMSPMA can easily be homo- and copolymerized with GTP, several polymers were synthesized. The polymers were synthesized similarly to previous GTP studies on linear block copolymers [ 28–33 ] and star polymers. [ 34–36 ] The polymerization catalyst, sol-vent, and initiator were added in a round-bottom fl ask and then the monomer(s) were syringed sequentially. No polymerization took longer than 30 min. More details are provided in the Supporting Information while all the syn-thesized polymers are listed in Table  1 . In the same table the gel permeation chromatography (GPC) and proton nuclear magnetic resonance ( 1 H NMR) spectroscopy data of all the polymers as well as their precursors are given.  The fi rst polymer was a TMSPMA chain growth poly mer (GPC traces shown in Figure  2 a) that had a number average molecular weight ( M n ) close to the Macromol. Rapid Commun. 2015,  36,  1806−1809 Figure 1.  GTP kinetics of TMSPMA. The theoretically calculated molecular weight and the  M n are shown as white and black tri-angles, respectively. Table 1.  Molecular weights and compositions of the TMSPMA-based (co)polymers and their precursors. No. Polymer structure Theor. MW a) [g mol −1 ] M n b) [g mol −1 ] M w / M n b) % mol TMSPMATheor. By NMR1 TMSPMA 15 3825 4380 1.08 100 100TMSPMA 15 - b -TMSPMA 15 7550 7640 1.07 100 1002 MMA 20 2102 3140 1.09 0 0MMA 20 - b -TMSPMA 20 7069 9030 1.05 50 453 TMSPMA 20 5067 5600 1.06 100 100TMSPMA 20 - b -MMA 20 7069 8400 1.05 50 514 TMSPMA 20 5067 5870 1.06 100 100TMSPMA 20 - star  c) 54100 1.19 N/A N/A a) Calculated as MW polymer = MW monomer × DP monomer + 100 g mol −1 (for the initiator fragment, an MMA group, that is attached at the end of the chain);  b) Determined using gel permeation chromatography with an RI detector which was calibrated using poly(methyl methacrylate) (PMMA) standards;  c) Cannot be theoretically calculated because the number of arms is not known and cannot be predicted. J. J. Chung et al.MacromolecularRapid Communicationswww.mrc-journal.de www.MaterialsViews.com1808 © 2015  The Authors. Published by WILEY-VCH Verlag GmbH &  Co.  KGaA, Weinheimtheoretically expected molecular weight (MW) and a narrow  M w / M n = 1.07. The second and third polymers, diblock copolymers of TMSPMA and MMA, were syn-thesized successfully, again proving that TMSPMA can easily be polymerized with GTP as the fi rst or the second block. From the GPC traces (Figure  2 b), it can be con-fi rmed that there is no termination after the formation of the fi rst block and the block polymers can be synthe-sized without any diffi culties. Also the  D s of the polymers decreased as the MW increased, as expected for a living polymerization method. This is shown in Table  1 , where the  D s of the second blocks were always lower than that of the fi rst blocks, the precursors to the copolymers. To this end, it should be pointed out that the  D s of the two diblock copolymers were very narrow ( M w / M n = 1.05) and matched the fi rst study [ 5 ] on TMSPMA polymer synthesis with living anionic polymerization.  The NMR results confi rmed that the % mol composition of the MMA- b -TMSPMA and the TMSPMA- b -MMA diblock copolymers were close to the targeted compositions (an NMR spectrum is given in the Supporting Information).  In addition to the linear TMSPMA-based homo- and copolymers, a star polymer was also synthesized using the “arm-fi rst” approach. In particular, a linear TMSPMA homopolymer was synthesized fi rst and then a bifunc-tional monomer (a crosslinker), ethylene glycol dimeth-acrylate, was added last to interconnect the linear homopolymer to form a star polymer. The  M n of the syn-thesized star homopolymer was about ten times higher than that of the corresponding linear precursor and the  D was equal to 1.19, which was acceptably narrow for a star polymer. The GPC traces of the star polymer and its precursor are shown in Figure  2 c. The peak on the left (of higher MWs) corresponds to the star polymer while the peak on the right represents the linear precursor that was not interconnected to the star polymer. This was expected for an “arm-fi rst” star polymer synthesis and it has been observed before. [ 34–43 ] At this point we would like to point out that, to the best of our knowledge, this is the fi rst time that a TMSPMA containing star polymer has been synthesized with the TMSPMA units being intact.  Finally, in order to confi rm that the trimethoxysilyl-functional group was unaffected by the polymerization, the star polymer was crosslinked to produce a gel with the addition of hydrochloric acid. The gel was formed instantly as can be seen in Figure  3 . This demonstrated the possibility of producing hybrids by GTP in a one-pot synthesis.  3.  Conclusions  TMSPMA (co)polymers were successfully synthesized using GTP method to produce well-defi ned (co)polymers. Both Macromol. Rapid Commun. 2015,  36,  1806−1809 Figure 2.  GPC traces a) of the TMSPMA 15 - b -TMSPMA 15 chain growth polymer, b) of the TMSPMA 20 - b -MMA 20 diblock copolymer, c) of the TMSPMA 20 - star homopolymer, and their corresponding precursors. Figure 3.  Gel formation in seconds after the addition of HCl in a TMSPMA 20 - star solution.MacromolecularRapid CommunicationsToward Hybrid Materials: Group Transfer Polymerization of 3-(Trimethoxysilyl)propyl Methacrylatewww.mrc-journal.de www.MaterialsViews.com 1809© 2015  The Authors. Published by WILEY-VCH Verlag GmbH &  Co.  KGaA, Weinheimlinear and star polymers were synthesized with  D s lower than 1.09 and 1.20, respectively. This opens up possibilities to produce more well-defi ned organic/inorganic hybrids.  Supporting Information  Supporting Information is available from the Wiley Online Library or from the author.  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Towards Hybrid Materials: Group Transfer Polymerization of 3-(Trimethoxylsilyl)propyl Methacrylate

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Towards Hybrid Materials: Group Transfer Polymerization of 3-(Trimethoxylsilyl)propyl Methacrylate

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