1、含贻贝粘附蛋白仿生粘合剂的设计、合成及性能研究IntroductionHarbin 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）。catecholHarbin Institute of TechnologyFigure Di
2、fferent effects of Dopa in the thread on the substrateIntroductionHarbin Institute of Technologycovalent bond interactionsNon-covalent bond interactionsIntroductionHarbin Institute of TechnologyApplicationsIdeal for watertight sealants and adhesives for ships1234Feature：excellent waterproof adhesive
3、 force and fast curingIdeal biomedical adhesive materialMultifunctional adhesive materials(PSAs,coatings)To improve performance of resulting polymerIntroductionHarbin Institute of TechnologyRelationship between publications and publication yearDate from Web of Science Searching Keywords：“catechol po
4、lymers”,“dopamine polymers”,“mussel-inspired polymers”,“poly(dopamine(meth)acrylamide)”,“poly(vinyl catechol)”.IntroductionHarbin Institute of TechnologyLee,S.B.et al.Biomacromolecules 2015,16(8),22652275.IntroductionHarbin Institute of TechnologyJeong,Y.K.et at.ACS Applied Materials&Interfaces 2017
5、,10(9),75627573.IntroductionHarbin Institute of TechnologyExperimentHarbin Institute of TechnologyAdvantages of acrylate matrix:Figure Synthesis strategies to obtain UV-reactive(meth)acrylic oligomers(R=H,CH3)Introduction High reactivity simple synthesis process Easy to modified UV reaction can be a
6、chievedHarbin Institute of TechnologyHOOHH2NCOOHOOOHOOHHNCOOHO1.Sodium Borate Na2CO3 pH82.1M HCl,pH2DOPADOPA-MAAMAAExperimentStep 1 Synthesis of L-Dopa acrylamide(L-DMA）13C NMR1H NMRFT-IRHarbin Institute of TechnologyStep 2 Synthesis of P(BA-co-DOPA-MAA)BADOPA-MAAHOOHHNCOOHOOO*xy0 wt.%5 wt.%10 wt.%1
7、5 wt.%20 wt.%30 wt.%Experiment Free 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 TechnologyOriginalOxidationFurther oxidizePolymers containing
8、catecholic groups are oxidized easily,first it oxidizes to dark semiquinones or quinones,and then to further oxidize to form cross-linked polymers.The FT-IR characteristic absorption peaks of benzene(1520 cm-1),amide(1658 cm-1)and phenolic hydroxyl(3345 cm-1)gradually increased.ExperimentHarbin Inst
9、itute of Technology130oC2hOptimum curing condition：130oC、2hTest method for adhesiveExperimentHarbin Institute of Technology15 wt.%DOPA-MAAMnMw0%213002260005%54004200010%77005000015%79004600020%66004100030%27007700steelAlPPPTFE Surface energysteelAlPPPTFEmN/m34.233.031.617.3The molecular weight of co
10、polymer was adjusted by changing the amount of initiator,and the adhesion on different substrates was investigated.ExperimentHarbin Institute of TechnologyWhen the amount of AIBN is 0.46%,the polymer showed the best bonding strengthAIBNMnMwMvPD0.115%300001205008180003.90.23%16000867004420005.10.46%1
11、4000780004900005.20.69%12000512001570004.20.92%7900464001550005.81.15%1400343001005004.6ExperimentHarbin Institute of TechnologyCoating 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.%0.77MPa1.11MPaTestin
12、g condition：55、24h，steelWaterproof adhesive on the market(steel plate test)ExperimentHarbin Institute of TechnologyAdvantages of acrylate matrix:Figure Synthesis strategies to obtain UV-reactive(meth)acrylic oligomers(R=H,CH3)Introduction High reactivity simple synthesis process Easy to modified UV
13、reaction can be achievedHarbin Institute of TechnologyExperimentGraphical Abstract rapid 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 th
14、e success of this technologyHarbin Institute of TechnologyExperimentScheme 1.Illustration of the fabrication process of L-DMA-GPC-MA polymer networks.Harbin Institute of TechnologyExperimentFig.3.FTIR spectra of the(a)UV uncured polymer and(b)UV cured polymer.1636cm-11636cm-1Harbin Institute of Tech
15、nologyExperimentFig.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 TechnologyExperimentFig.5.Storage modulus(G)of L-DMA-GPCL-MA polymer.Table 1.Mechanical properties of L-DMA-GPCL-MA polymera:Crosslink dens
16、ity(n):Where n is crosslink density,G is the polymer storage modulus at temperature Tg+40 oC,R is the universal gas constant and T is the absolute temperature(K).Harbin Institute of TechnologyExperimentTable 2.Adhesion strength of L-DMA-GPCL-MA polymer bonding different substrates.Fig.6.Adhesion str
17、ength of L-DMA-GPCL-MA polymer.Harbin Institute of TechnologyExperimentFig.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 TechnologyExperimentFig.8.Hydrolytic degradation of L-DMA-GPCL-MA polymers,in PBS solution at 37oC.Fig.9.Hyd
18、rolytic 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 TechnologySummarya new type of mussel-inspired adhesive possessing high adhesion strength and fast d
19、egradation performance was designed via UV polymerization,40s of UV exposure was enough to achieve a maximum degree of UV polymerization.poly(L-DMA-GPCL-MA)shows excellent adhesive behaviors,the maximum adhesion of polymer on steel substrate was 3.2 0.38 MPa,it also is able to stick to the low-energy surface substrates including Polypropylene(PP)and Polytetrafluoroethylene(PTFE).poly(L-DMA-GPCL-MA)shows faster degradation,the polymer lost around 40%of their initial weight after 48 day immersing into PBS(0.01 M,pH=7.3).
