Facile synthesis of gradient copolymers enabled by droplet-flow photo-controlled reversible deactivation radical polymerization

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  • ReceivedDec 18, 2020
  • AcceptedJan 18, 2021
  • PublishedMar 23, 2021



the National Natural Science Foundation of China(21704016,21971044)


This work was supported by the National Natural Science Foundation of China (21704016, 21971044).

Interest statement

The authors declare no conflict of interest.

Supplementary data

The supporting information is available online at http://chem.scichina.com and http://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.


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  • Figure 1

    Gradient copolymerization conducted under computer-aided droplet-flow conditions. (a) General setup of the flow system; (b) three gradient tendencies and corresponding necklace models generated in this work (color online).

  • Figure 2

    Process for the generation of gradient copolymers via the droplet-flow photopolymerization with pre-diffusion before light irradiation (method A) (color online).

  • Figure 3

    Investigation on the formation of gradient copolymers with pre-diffusion before polymerization (method A). (a–d) Kinetic plots for the copolymerization of DMA and BA. (e–h) Simulated diagrams of instantaneous BA contained in copolymers (Finst,BA) as a function of total conversion. From left to right, VA/VB=1:0, 1:1, 1:2, 1:4, respectively (color online).

  • Figure 4

    Process for the generation of gradient copolymers via the droplet-flow photopolymerization without pre-diffusion before light irradiation (method B) (color online).

  • Figure 5

    Kinetic plots for the copolymerization of DMA and BA without pre-diffusion before photopolymerization (method B). From (a) to (c), VA/VB=1:1, 1:2, 1:4, respectively (color online).

  • Figure 6

    Investigation on Tg of copolymers with different sequences by DSC measurement. (a) The derivatives of DSC heating curves for PDMA-r-PBA, PDMA-b-PBA, and PDMA-grad-PBA. (b–d) Derivative of DSC heating curves for PDMA-grad-PBA prepared with (blue) and without (yellow) pre-diffusion of BA during droplet-flow photopolymerization (color online).

  • Figure 7

    Synthesis of copolymers with different gradient tendencies and chemical compositions. (a) Without and (b) with pre-diffusion before polymerization; (c) V-shape gradient copolymer synthesized without pre-diffusion (color online).

  • Figure 8

    Synthesis of (PDMA-grad-PBA)-b-PDMA via the chain-extension from the macro-initiator of PDMA-grad-PBA (color online).

  • Figure 9

    Rh and PDI of NIPAm/BA copolymers in H2O/methanol (1:9, V/V) at different temperatures (squares for gradient sequence, circles for random sequence, triangles for block sequence) (color online).

  • Table 1   Synthesis of DMA/BA gradient copolymers with pre-diffusion before photopolymerization (method A) a)



    Flow rates of streamsA/B (μL/min)

    Residence time (min)

    Conv. of DMA (%)

    Conv. of BA (%)

    Mn,calc b) (kDa)

    Mn,SEC b) (kDa)

    Đ b)





























    1:4 c)









    1:4 c)








    All reactions were performed with [DMA]/[BA]/[CTA]/[PC]=100:100:1:0.01, [DMA]=1 M at room temperature. A 23 W white LED bulb was used as light source. Residence time is equal to the exposure time of light irradiation. b) Mn,calc was determined based on monomer conversions, Mn,SEC and Đ were determined by SEC measurement. c) [DMA]/[BA]/[CTA]/[PC]=67:133:1:0.01, [DMA]=0.67 M.


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