1、含貽貝粘附蛋白仿生粘合劑的設(shè)計(jì)、合成及性能研究含貽貝粘附蛋白仿生粘合劑的設(shè)計(jì)、合成及性能研究2IntroductionHarbin Institute of TechnologyFigure （A）The mussel sticks to the substrate through the thread of its feet；（B）Distribution of mussel foot proteins (Mfps)；（C）Amino acid sequences of Mfp-1, Mfp-3 and Mfp-5（Y：Dopa、K：lysine）。catechol4Introduction

2、Harbin Institute Harbin Institute of TechnologyFigure Different effects of Dopa in the thread on the substrate3IntroductionHarbin Institute of TechnologyHarbin Institute of Technologycovalent bond interactionsNon-covalent bond interactions4IntroductionHarbin Institute of TechnologyHarbin Institute o

3、f TechnologyApplicationsIdeal for watertight sealants and adhesives for ships1234Feature：excellent waterproof adhesive force and fast curingIdeal biomedical adhesive materialMultifunctional adhesive materials (PSAs, coatings)To improve performance of resulting polymer5IntroductionHarbin Institute of

4、 TechnologyHarbin Institute of TechnologyRelationship between publications and publication yearDate from Web of Science Searching Keywords：“catechol polymers”, “dopamine polymers”, “mussel-inspired polymers”, “poly(dopamine(meth)acrylamide)”, “poly(vinyl catechol)”.6IntroductionHarbin Institute of T

5、echnologyHarbin Institute of TechnologyLee, S. B. et al. Biomacromolecules 2015, 16 (8), 22652275.7IntroductionHarbin Institute of TechnologyHarbin Institute of TechnologyJeong, Y. K. et at. ACS Applied Materials & Interfaces 2017, 10 (9), 75627573.8IntroductionHarbin Institute of TechnologyHarbin I

6、nstitute of TechnologyExperimentHarbin Institute of TechnologyHarbin Institute of TechnologyAdvantages of acrylate matrix: Figure Synthesis strategies to obtain UV-reactive (meth)acrylic oligomers (R=H, CH3)10IntroductionHigh reactivitysimple synthesis processEasy to modifiedUV reaction can be achie

7、vedHarbin Institute of TechnologyHarbin Institute of TechnologyDOPADOPA-MAAMAA11ExperimentStep 1 Synthesis of L-Dopa acrylamide (L-DMA）13C NMR1H NMRFT-IRHarbin Institute of TechnologyHarbin Institute of TechnologyStep 2 Synthesis of P(BA-co-DOPA-MAA)BADOPA-MAA0 wt.%5 wt.%10 wt.%15 wt.%20 wt.%30 wt.%

8、12ExperimentFree radical polymerization of butyl acrylate (BA) and DOPA-MAA in vacuum without oxygen.The following figure shows the dissolution state of polymer in THF with different DOPA-MAA contents.Harbin Institute of TechnologyHarbin Institute of TechnologyOriginalOxidationFurther oxidizePolymer

9、s containing catecholic groups are oxidized easily, first it oxidizes to dark semiquinones or quinones, and then to further oxidize to form cross-linked polymers.13The FT-IR characteristic absorption peaks of benzene (1520 cm-1), amide (1658 cm-1) and phenolic hydroxyl (3345 cm-1) gradually increase

10、d.ExperimentHarbin Institute of TechnologyHarbin Institute of Technology130oC2hOptimum curing condition：130oC、2hTest method for adhesive14ExperimentHarbin Institute of TechnologyHarbin Institute of Technology15 wt. %DOPA-MAAMnMwPD0%2130022600010.65%5400420007.710%7700500006.515%7900460005.820%660041

11、0006.230%270077002.8steelAlPPPTFE Surface energysteelAlPPPTFEmN/m34.233.031.617.315The molecular weight of copolymer was adjusted by changing the amount of initiator, and the adhesion on different substrates was investigated.ExperimentHarbin Institute of TechnologyHarbin Institute of TechnologyWhen

12、the amount of AIBN is 0.46%, the polymer showed the best bonding strength16AIBNMnMwMvPD0.11590.23%16000867004420005.10.46%14000780004900005.20.69%12000512001570004.20.92%7900464001550005.81.15%1400343001005004.6ExperimentHarbin Institute of TechnologyHarbin Institute of Technolog

13、yCoating adhesive in the waterCuring in the waterpH=8pH=4P(BA-DOPA-MAA)-15wt.%0.42MPa0.22MPaTesting condition：37、11day，steelIO4-Mn3+P(BA-DOPA-MAA)-15wt.%0.77MPa1.11MPaTesting condition：55、24h，steelWaterproof adhesive on the market (steel plate test)17ExperimentHarbin Institute of TechnologyHarbin In

14、stitute of TechnologyAdvantages of acrylate matrix: Figure Synthesis strategies to obtain UV-reactive (meth)acrylic oligomers (R=H, CH3)18IntroductionHigh reactivitysimple synthesis processEasy to modifiedUV reaction can be achievedHarbin Institute of TechnologyHarbin Institute of TechnologyExperime

15、nt19Graphical Abstractrapid through cure, low energy requirements, room-temperature treatment, non-polluting and solvent-free formulations.UV polymerization has many advantages:All these characteristics can allow cost reduction and explain the success of this technologyMussel-Inspired Polymer: A Pho

16、tocurable and Degradable Polymer Network for AdhesivesHarbin Institute of TechnologyHarbin Institute of TechnologyExperiment20Scheme 1. Illustration of the fabrication process of L-DMA-GPC-MA polymer networks.Harbin Institute of TechnologyHarbin Institute of TechnologyExperiment21Fig. 3. FTIR spectr

17、a of the (a) UV uncured polymer and (b) UV cured polymer.1636cm-11636cm-1Harbin Institute of TechnologyHarbin Institute of TechnologyExperiment22Fig. 4. The relative concentration of C=C group from L-DMA-GPCL-MA with curing The relative concentration of C=C bond (Rel. C UV)Harbin Institute of Techno

18、logyHarbin Institute of TechnologyExperiment23Fig. 5. Storage modulus (G) of L-DMA-GPCL-MA polymer.Table 1. Mechanical properties of L-DMA-GPCL-MA polymera: Crosslink density (n):Where n is crosslink density, G is the polymer storage modulus at temperature Tg + 40 oC, R is the universal gas constant

19、 and T is the absolute temperature (K).Harbin Institute of TechnologyHarbin Institute of TechnologyExperiment24Table 2. Adhesion strength of L-DMA-GPCL-MA polymer bonding different substrates.Fig. 6. Adhesion strength of L-DMA-GPCL-MA polymer.Harbin Institute of TechnologyHarbin Institute of Technol

20、ogyExperiment25Fig. 7. TG and DTG curves of L-DMA-GPCL-MA polymer.Table 3.TG and DTG results of L-DMA-GPCL-MA polymer.Harbin Institute of TechnologyHarbin Institute of TechnologyExperiment26Fig. 8. Hydrolytic degradation of L-DMA-GPCL-MA polymers, in PBS solution at 37oC.Fig. 9. Hydrolytic degradation images of L-DMA-GPCL-MA polymers, in PBS solution at 37oC.Where W0 is the weight of samples before degradation, and W1 is the weight of samples after degradation.Harbin Institute of TechnologyHarbin Institute of TechnologyS