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Ring-Opening Metathesis Polymerization of Cis-5-Norbornene-Endo-2,3- Dicarboxylic Anhydride Derivatives Using the Grubbs Third Generation Catalyst*

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Ring-Opening Metathesis Polymerization of Cis-5-Norbornene-Endo-2,3- Dicarboxylic Anhydride Derivatives Using the Grubbs Third Generation Catalyst* Chinese Journal of Polymer Science Vol. 35, No. 1, (2017), 36−45 Chinese Journal of Polymer Science © Chinese Chemical Society Institute of Chemistry, CAS Springer-Verlag Berlin Heidelberg 2017 Ring-opening Metathesis Polymerization of Cis-5-norbornene-endo-2,3- dicarboxylic Anhydride Derivatives Using the Grubbs Third * Generation Catalyst Ji-xing Yang, Li-xia Ren** and Yue-sheng Li School of Materials Science and Engineering and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300072, China Abstract A series of cis-5-norbornene-endo-2,3-dicarboxylic anhydride (NDCA, M1) derivatives (M2−M4) with different types of nonpolar substituted groups were synthesized and characterized by 1H/13C-NMR and mass spectrometry (MS). Ring- opening metathesis polymerization (ROMP) of these monomers using the Grubbs third generation catalyst (G3) generated high molecular weight polymers with much improved solubility compared with the NDCA’s homopolymer. It was found that the solubility of these polymers increased with increased substituent’s steric hindrance. The living polymerization of NDCA derivative containing the bulkiest substituent (M4) catalyzed by G3 in tetrahydrofuran was confirmed by the kinetic studies with low polydispersity indices (PDI) (< 1.30). By using sequential ROMP, well-defined diblock copolymers containing anhydride groups were synthesized. Keywords Living polymerization; Ring-opening metathesis polymerization; Amphiphilic block copolymer; Anhydride group Electronic Supplementary Material Supplementary material is available in the online version of this article at http://dx.doi.org/10.1007/s10118-017-1873-1. INTRODUCTION Over the past two decades, ring-opening metathesis polymerization (ROMP) has become a powerful and broadly applicable method for synthesizing macromolecular materials[1]. Especially, ROMP has proven to be a versatile method for creating well-defined block copolymers (BCPs) with low polydispersity indices (PDIs) due to its living nature[2, 3]. The advent of ruthenium (Ru) based catalysts, such as the commercial Grubbs catalysts, which exhibit a remarkable functional group tolerance, makes ROMP particularly valuable for synthesizing highly functionalized polymer materials[4]. Thus far, norbornene derivatives substituted with many kinds of polar groups including amide[5], ester[4, 6], and hydroxyl groups[7] have been successfully polymerized. Through sophisticated molecular design, norbornene derivatives containing more polar groups, such as carboxys[8], amines[9], and even sulfonate groups[10−12], can be also effectively polymerized. For instance, Sanda and Masuda et al. have achieved direct polymerization of norbornene monomers carrying amino groups or carboxyl groups without protection utilizing the Grubbs second generation catalyst (G2) in good yields by incorporating amino acid spacers between the polar groups and norbornene skeleton, which maybe prevent amino groups or carboxyl groups from interacting with the ruthenium center[13]. * This work was financially supported by the National Natural Science Foundation of China (Nos. 21234006 and 21574098). ** Corresponding author: Li-xia Ren (任丽霞), E-mail: [email protected] Received August 12, 2016; Revised September 9, 2016; Accepted September 12, 2016 doi: 10.1007/s10118-017-1873-1 ROMP of Cis-5-norbornene-endo-2,3-dicarboxylic Anhydride Derivatives 37 Polymers containing anhydride group are functional polymers due to the reactivity of anhydride groups and show wide applications in processing, separation and so on[14, 15]. Maleic anhydride modified polypropylene (MA-PP) is the most important commercially functionalized PP polymer for its low cost, high activity, and good processing ability[16]. The anhydride group can be transformed into carboxylic acid or carboxylate, which could be used in separation techniques[17]. The anhydride group can also react with other functional groups such as amino group, which could further broaden its application[18]. However, the preparation of polymers containing anhydride group including post-modification, copolymerization with other monomers is limited. ROMP has been utilized in preparation of polymers containing anhydride group[18]. Buchmeiser and coworkers reported the synthesis of cross-linked polymer containing anhydride group by ROMP of cis-endo-5-norbornene-2,3- dicarboxylic anhydride (NDCA, M1 in Scheme 1) and monomer containing bi-norbornene followed by hydrolysis. The resultant polymer material showed applications in solid-phase extraction (SPE) as well as for air and water clean-up[19]. Grubbs et al. reported on the homo-polymerization of NDCA monomers, however the product was insoluble in the solvent[20]. To date, synthesis of homo- and block copolymers containing anhydride group by controlled/living polymerization is very challenging due to the high polarity of anhydride group. In this study, non-polar substituent was introduced into NDCA to improve the solubility of the corresponding homopolymer (Scheme 1). Different substituents were selected in the preparation of NDCA derivatives to study the size/steric hindrance effect of the substituent on the solubility of polymer containing the anhydride as well as the polymerization behavior. Furthermore, block copolymers containing anhydride groups with well-defined structure were prepared. Scheme 1 Monomers synthesized via D-A reaction and its homopolymerization EXPERIMENTAL Materials All materials were obtained from Sigma-Aldrich or TCI and used without further purification except otherwise specified. Anhydrous solvents used in this work were purified by Solvent Purification System (SPS) purchased from Mbraun. Grubbs third generation catalyst RuCl2(3-bromopyridine)2(H2IMes)(CHPh) (G3, H2IMes = N,N- dimesityl-4,5-dihydroimidazol-2-ylidene), synthesized by the method reported previously[21−23], were stored and weighted in the glovebox. Fresh cyclopentadiene (CPD) was cracked slowly from dicyclopentadiene at 168 °C and collected at 0 °C. Phenylmaleic anhydride (PMA)[24] and 9,10-dihydro-9,10-ethenoanthracene-11,12- dicarboxylic anhydride (DHEADCA)[25, 26] were prepared according to literatures with modification (see Supporting Information, SI). 38 J.X. Yang et al. Characterizations All experimental procedures involving the preparation of air- and/or moisture-sensitive compounds were conducted in Mbraun glovebox or under a nitrogen (N2) atmosphere using standard Schlenk technique unless otherwise noted. Gel permeation chromatography (GPC) was performed on a Waters 1525 instrument with tetrahydrofuran (THF) as eluent at a flow rate of 1.0 mL/min at 35 °C. Linear polystyrene (PS) standards (Easi- Cal PS-1, PL Ltd.) were used as calibration. 1H and 13C-NMR spectra were recorded on a Bruker-400 MHz spectrometer (399.65 MHz for 1H and 100.40 MHz for 13C, respectively) at 25 °C. Mass spectra were recorded on Quattro Premier XE spectrometer with Ionization Mode (ESI). Differential scanning calorimetry (DSC) measurements were performed on a Netzsch 204F1 in nitrogen atmosphere. The samples were heated up and cooled down at a rate of 10 K/min. Glass transition temperature (Tg) was taken from the second heating run and was read as the midpoint of change in heat capacity. Thermal gravimetric analysis (TGA) was performed using a SDTQ 600 TGA Instrument under nitrogen flow at a heating rate of 10 K/min from 40 °C to 800 °C. Synthesis of M2 Monomer M2 was synthesized according to previous reports with modification[27, 28]. Methyl maleic anhydride (MMA) (10 g, 89 mmol) and benzene (40 mL) were added into a round bottom flask (50 mL) equipped with a magnetic stirrer. Freshly cracked CPD (15 mL, 4 eq. of MMA) was added into the flask. The mixture was stirred at room temperature (R.T.) for 20 h followed by reacting at 50 °C for additional 5 h. The solvent was evaporated under vacuum, and a white solid was obtained. The pure product was obtained through recrystallization from 1 ethyl ether/hexane for twice (14.5 g, 92%). H-NMR (400 MHz, CDCl3, δ): 6.35 (dd, 1H), 6.26 (dd, 1H), 3.42−3.43 (br m, 1H), 3.10 (d, 1H), 3.00 (br m, 1H), 1.76−1.82 (m, 2H), 1.59 (s, 3H); 13C-NMR (100.4 MHz, CDCl3, δ): 174.90, 170.90, 137.20, 135.20, 53.70, 53.40, 52.00, 50.60, 46.60, 21.30; MS (ESI), m/z theoretical + Calc. for [C10H10O3 + Na] 201.06; Found 201.10. Synthesis of M3 Monomer M3 was synthesized from PMA and CPD following the similar procedures as M2[29, 30]. The yield was l 71%. H-NMR (400 MHz, CDCl3, δ): 7.60−7.30 (m, 5H), 6.46 and 6.39 (m, 2H), 3.88 (d, 1H), 3.61 (m, 1H), 13 3.55 (m, 1H), 1.80−1.68 (m, 2H); C-NMR (100.4 MHz, CDCl3, δ): 172.60, 170.70, 137.28, 136.94, 136.35, + 129.19, 128.42, 126.93, 62.62, 53.46, 52.62, 50.96, 46.92; MS (ESI), m/z theoretical Calc. for [C15H12O3 + Na] 263.08; Found 263.2. Synthesis of M4 Monomer M4 was synthesized as follows. 9,10-Dihydro-9,10-ethenoanthracene-11,12-dicarboxylic anhydride (DHEADCA) (8 g, 29.2 mmol), dissolved in DCM (50 mL), were added into a 100 mL round bottom flask equipped with a magnetic stirrer. CPD (30 mL, 364 mmol) was added and stirred at R.T. for 12 h. During the reaction, white solids were precipitated from the solution. Another 14 mL of CPD (170 mmol) was added and stirred overnight. The off-white solid was filtered and washed with abundant hexane. The product was purified by recrystallizing from hexane/DCM mixture as off-white microcrystalline. After dried under vacuum for 10 h, l 6.5 g product was obtained with yield of 63%. H-NMR (400 MHz, CDCl3, δ): 7.11−7.35 (m, 8H), 6.41 (m, 2H), 13 4.64 (s, 2H), 3.01 (m, 1H), 1.19 (d, 1H), 0.18 (d, 2H); C-NMR (100.4 MHz, CDCl3, δ): 173.00, 141.40, 141.20, 140.00, 127.60, 127.40, 125.40, 125.30, 67.40, 48.60, 47.90, 47.50; MS (ESI), m/z theoretical Calc.
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