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. 2019 Dec 6;9(69):40455-40461.
doi: 10.1039/c9ra08155k. eCollection 2019 Dec 3.

Mild polyaddition and polyalkylation based on the carbon-carbon bond formation reaction of active methylene

Caicai Jiao  1   2 , Lilong Gao  1 , Bing Yu  2   3   4 , Hailin Cong  1   2   4 , Youqing Shen  1   2   5
Affiliations

Mild polyaddition and polyalkylation based on the carbon-carbon bond formation reaction of active methylene

Caicai Jiao et al. RSC Adv. .

Abstract

The Michael addition and alkylation reaction of active methylene compounds (AMCs) with two active hydrogens had been investigated extensively in organic chemistry, while the polymerization of AMCs had few studies. Herein, we reported active methylene-based polyaddition and polyalkylation catalyzed via an organic superbase under ambient conditions. A model polymerization was first conducted between ethylene glycol diacrylate (EGDA) and methyl cyanoacetate (MCA). The molecular weight (M w) of the model polymer was up to 50 500 g mol-1 with a high yield (99%). Eight AMCs were selected and a high-throughput parallel synthesizing instrument (HTPSI) was used to synthesize semi-library polymers of AMCs and EGDA via a Michael type polyaddition. The obtained AMC-based polymers had low cell cytotoxicity. Elastomers with cyanogen groups could be prepared using trimethylolpropane triacrylate (TMPTA) as a crosslinker. Furthermore, three dihalogen compounds were explored to polymerize with MCA and malononitrile via alkylation reactions. The pendent cyanogen or ester groups of the polymers could be reduced by lithium aluminum hydride. Novel polymer families were constructed based on the polyaddition and polyalkylation of AMCs.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Fig. 1
Fig. 1. (A) Model polymerization of EGDA and MCA. The obtained polymer was named P(MCA-EGDA). (B) 1H NMR spectra of the model reaction catalysed by TEA, DMAP and DBU (* residual solvent).
Fig. 2
Fig. 2. (A) 1H NMR spectra of the model polymerization with different times. (B) Conversion of CC calculated by 1H NMR.
Fig. 3
Fig. 3. The gel permeation chromatography (GPC) curve of the model polymer, P(MCA-EGDA).
Fig. 4
Fig. 4. Degradation of P(MCA-EGDA) in phosphate buffered saline (10 mM, pH = 7.4, 37 °C).
Fig. 5
Fig. 5. Cell viability of P(MCA-EGDA) against the HeLa cells.
Fig. 6
Fig. 6. (A) Polyalkylation of MCA with BDC. The obtained polymer was named P(MCA-BDC). (B) 1H NMR spectrum and (C) 13C NMR spectrum of P(MCA-BDC). (D) GPC curve of P(MCA-BDC).
Fig. 7
Fig. 7. (A) Reduction product of P(MCA-BDC): R-P(MCA-BDC). (B) 1H NMR spectrum of R-P(MCA-BDC). (C) GPC curve of R-P(MCA-BDC). (D) FT-IR spectra of P(MCA-BDC) and R-P(MCA-BDC).
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