| Catalytic chain transfer polymerization can prepare polymer with terminal double bonds and we can use this feature to design molecular.At first,hydrophilic chain segment can be prepared via catalytic chain transfer polymerization,which can be as a macromolecular monomer to be polymerized with hydrophobic monomer to get macromolecular surfactant with end of double bond via Catalytic chain transfer polymerization.This article prepared three series of macromolecular surfactant CSF,BSF and ASF via Catalytic chain transfer polymerization,which were applied to the WPUA polymerization,and the influence of macromolecular surfactant on properties of emulsion and latex film were studied.The main research in this article as follows:(1)A series of macromolecular surfactants(CSF)were prepared via Catalytic chain transfer polymerization,using dimethyl aminoethyl methacrylate(DM)as hydrophilic monomer,alkyl methacrylate with different side chain length as hydrophilic monomer,2,2-azodiisobutyronitrile(AIBN)as initiator and cobaloxime boron fluoride(CoBF)as catalytic chain transfer agent,and random copolymer surfactant(SF-CO)which was synthesized via free radical copolymerization as comparison.(1H-NMR)and(FT-IR)indicated the presence of terminal double bonds on the polymer chains.GPC tests showed that CSF molecular weight increased from 2×10~3 to 4×10~3,and their polydispersity index(PDI)increased from 1.2 to 1.7 with increase of number of hydrophobic monomer side chain carbon atom from 1 to 12.While SF-CO molecular weight was 1.25×104,and the polydispersity index(PDI)was 1.93,which showed CCTP can effectively reduce the molecular weight and polydispersity index(PDI).Thermogravimetric(TG)shown that there was a double bond thermal decomposition weightlessness rate peak in CSF,and CSF thermal stability was lower than the SF-CO.Surface tension of CSF decreased firstly and then increased with the increase of side chain length and the ?CMC of CSF4 was low to 33.27 mN/m;while the CMC decreased from 0.31g/L to 0.19g/L in turn.Whereas the ?CMC of SF-CO was 37.36 mN/m and CMC was 0.16g/L,which demonstrated surface activity of CSF was higher than SF-CO.With the increase of length of ester chain alkyl methacrylate,polymer particle size decreased and then increased.Transmission electron microscopy(TEM)showed that SF-CO,CSF4 and CSF8 respectively were reticula,vermicular and spherical micelles.(2)A series of macromolecular surfactants(BSF)with different proportion of hydrophilic and hydrophobic monomers were prepared using dimethyl aminoethyl methacrylate(DM)as hydrophilic monomer and butyl methacrylate(BMA)as hydrophobic monomers.(1H-NMR)and(FT-IR)indicated the presence of terminal double bonds on the polymer chains.GPC tests showed that with increase of hydrophobic monomers BMA content,molecular weight increased from 1.8×10~3 to 3.6×10~3 and polydispersity index(PDI)increased from 1.26 to 1.55.Surface tension of BSF decreased and then increased with increase of BMA content,and surface tension of BSF4 was low to 32.12 mN/m,while CMC of BSF decreased from 0.51g/L to 0.19g/L.Polymer particle size decreased and then increased,which of BSF4 was low to 86.7nm.TEM showed BSF1 and BSF4 were vesicular and spherical micelles respectively.(3)Using dimethyl aminoethyl methacrylate(DM)and acrylamide(AM)as hydrophilic monomer and butyl methacrylate(BMA)as hydrophobic monomers,a series of macromolecular surfactants(ASF)with different content of AM hydrophilic monomers were prepared.(1H-NMR)and(FT-IR)indicated the presence of terminal double bonds on the polymer chains.GPC tests showed that ASF molecular weight increased from 3.3×10~3 to 5.2×10~3,and polydispersity index(PDI)increased from 1.47 to 1.76 with increase of AM hydrophilic monomers content.The surface tension of ASF increased with increase content of AM and the surface tension and ?CMC of ASF1 respectively were low to31.87 mN/m and 0.21 g/L.Polymer particle size increased,which of ASF3 was low to 72.2nm.TEM showed ASF3 was spherical micelles.(4)Three series of polymeric surfactants(CSF,BSF,ASF)and random copolymer surfactant(SF-CO)were applied to the WPUA emulsion polymerization.Phase inversion point tests showed that water conten in phase inversion point of PU-A pre-emulsion with CSF4,BSF4 and ASF3 were lowest,which respectively were 43%,38% and 30%,and corresponding WPUA solid content were highest,which respectively were 40%,42% and 43%,due to surfactant arranged in the oil-water interface when in phase inversion process,which formed a strong interfacial film,so surfactant with appropriate structure could made the PIP arrived early.PU-A pre-emulsion with SF-CO maximum water content in phase inversion point was 68% and solid content was 25%.Particle size test indicate that WPUA-CSF4,WPUA-BSF4,WPUA-ASF3 particle were smallest.Transmission electron microscopy(TEM)showed that dispersion of WPUA-CSF4,WPUA-BSF4 and WPUA-ASF3 were better than WPUA-SF-CO.Rheological tests showed that tan? of WPUA-CSF4,WPUA-BSF5 and WPUAASF3 emulsion had changed little with oscillation frequency increase and the emulsion performanced for viscous behavior,while tan? of WPUA-SF-CO latex reduced with oscillation frequency increase and the emulsion turned from viscous behavior to the elastic behavior.(5)Attenuated Total internal Reflectance Fourier Transform Infrared spectroscopy(ATR-FT-IR)showed that group in film distributed homogeneous,while WPUA-SF-CO were unhomogeneous.AFM showed that WPUA-CSF4 film surface morphology had little difference between after immersed into and before immersed into,while WPUA-SF-CO film morphology had obviously change after Immersed into,which demonstrated that migration was prevented by using polymeric macromolecular surfactant that were synthesized via Catalytic chain transfer polymerization.Mechanics performance analysis showed that performance of WPUA-CSF4 was better than WPUA-SF-CO.Water absorption of latex film showed that WPUA-CSF4,WPUA-BSF4 and WPUA-ASF3 had lower water absorption,which were 8.6%?7.3% and 6.5% respectively,and contact Angle were 96.3°,99.4° and 98.4° respectively,while WPUA-SF-CO water resistance was worst,which water absorption rate and the contact Angle were 31.2% and 72°.Thermogravimetric(TG)showed that WPUA-SF-CO was unstable compared to latex films which were prepared via catalytic chain transfer polymerization. |
PDF Full Text Request