Fabrication of Quaternary Ammonium Chloride-functionalized Poly hydroxyurethane Films

Transcription

1 Fabrication of Quaternary Ammonium Chloride-functionalized Poly hydroxyurethane Films Hiroyuki Matsukizono Takeshi Endo Poly hydroxyurethane s PHUs were synthesized by the polyaddition of, -oxybis methylene bis ethyl-, -propanediol DTMP -derived bifunctional six-membered cyclic carbonate DTMPC and diamines via non-phosgene derivative and non-isocyanate routes and then chemically modified to design quaternary ammonium chloride QAC -functionalized PHU films for antimicrobial applications. The reaction of DTMP with excess amounts of diphenyl carbonate DPC, which is obtainable via non-phosgene derivative routes, effectively undergoes transesterification at to give DTMPC in high yield. The reaction of DTMPC with a subtle excess of diamines affords PHUs with well-controlled molecular weights and polydispersities. The hydroxyl side chains of these PHUs can be modified with chloroacetyl chloride to afford chloroacetylated PHUs and subsequently reacted with N, N -dimethyl-n-octylamine DMOA to easily give QACfunctionalized PHUs. On the other hand, the reaction of the chloroacetylated PHUs with N, N, N, N - tetramethyl-, -diaminohexane TMDAH cross-linkers conducts the quaternization and simultaneously forms networked structures, which affords QAC-functionalized PHU films in one step. In particular, the use of mol % of TMDAH with respect to chloroacetyl groups gives a self-supported film with well transparency and higher thermal stability. Furthermore, remaining chloroacetyl groups of the films can be modified with DMOA to afford PHU films with dual QAC moieties having the positively-charged surfaces with a zeta potential of mv. JSR TECHNICAL REVIEW No.123/2016 1

2 Scheme Synthesis of QAC-functionalized PHUs from DTMP by four steps: transesterification, polyaddition, chloroacetylation and quaternization. i equiv. of DPC,, h. ii equiv. of aliphatic diamines, DMF,, h. iii equiv. of chloroacetyl chloride, equiv. of pyridine, to r. t., overnight, iv equiv. of DMOA, DMF,, h. Scheme Fabrication of QAC-functionalized PHU films QAC-Film via quaternization by TMDAH cross-linkers and subsequent modification with DMOA to form PHU films with dual QAC moieties QAC -Film. 2 JSR TECHNICAL REVIEW No.123/2016

3 M M M M M M M M M M M M M M M M M M Figure The effect of DPC DTMP feed ratios on the conversion of DTMP left axis and the selectivity of DTMPC formation right axis after the DTMP DPC solutions were reacted at for h. Figure Time-course analysis of the polymerization of DTMPC and C H with different DTMPC C H feed ratios in DMF at. The C H DTMPC feed ratios were a or b. Mn and Mw Mn were calculated by SEC traces and plotted as a function of reaction time. M M M M M M JSR TECHNICAL REVIEW No.123/2016 3

4 Figure H NMR spectrum of p DTMPC-C H in CD OD. The PHU was synthesized from DMF solution of DTMPC and C H C H DTMPC. Table Characterization of PHUs synthesized from DTMPC and diamines with different numbers of methylene spacers H N-R-NH at a diamine DTMPC feed ratio of before after chemical modifications M M M f M M M f M f f M M M f M M M n M M M M M M 4 JSR TECHNICAL REVIEW No.123/2016

5 Figure H NMR spectrum of p DTMPC-C H -QAC in CD OD. p DTMPC-C H was synthesized from DMF solution of DTMPC and C H C H DTMPC and then subsequently chloroacetylated followed by reacted with DMOA. JSR TECHNICAL REVIEW No.123/2016 5

6 Table E. A. results of PHU films prepared with mol% of TMDAH QAC-Film and PHU film after modification of DMOA QAC -Film. Figure a-c Photographs of PHU films prepared from p DTMPC-C -Cl and a different amount of TMDAH. The mole factions of TMDAH were a, b, c, d or e mol% with respect to the chloroacetyl groups of the PHU unit. Figure Characterization of QAC-Films prepared by the reaction of p DTMPC-C H -Cl with different amounts of TMDAH. a UV Vis. -NIR absorption spectra. Absorbance was converted to transmittance. b TGA profiles. TMDAH were black line, red line, blue line, green line, orange line or mol purple line with respect to the chloroacetyl groups of the PHU unit. 6 JSR TECHNICAL REVIEW No.123/2016

7 J. App. Polym. Sci 132 RSC Adv 5 J. Polym. Sci., Part A: Polym. Chem 54 Figure Photograph of QAC -Film prepared by the reaction of QAC-Film with DMOA in DMF at for h. The QAC-Film was prepared at mol% of TMDAH. Figure TGA profiles of QAC-Film prepared from p DTMPC-C H -Cl with mol % of TMDAH before after the secondary modification with DMOA. Macromolecules 46 RSC Adv 3 Eur. Polym. J 49 Green Chem 13 Green Chem 17 J. Polym. Sci. Part A: Polym. Chem 52 Polymer 54 J. Polym. Sci. Part A: Polym. Chem 45 J. Polym. Sci. Part A: Polym. Chem 45 Green Chem 7 J. Polym. Sci. Part A: Polym. Chem 43 J. Polym. Sci. Part A: Polym. Chem 43 J. Polym. Sci. Part A : Polym. Chem J. Appl. Polym. Sci 132 RSC Adv 4 Green Chem 16 JSR TECHNICAL REVIEW No.123/2016 7

8 ü Green Chem 15 ü React. Funct. Polym 71 Polym. Chem 5 J. Polym. Sci. Part A: Polym. Chem 39 J. Polym. Sci. Part A: Polym. Chem 39 Macromolecules 47 Biomacromolecules 14 Macromolecules 46 Adv. Mater 24 J. Mater. Sci. : Mater. Med 22 J. Funct. Biomater 4 Macromol. Rapid Commun 27 ACS Catal 3 J. Phys. Chem. C 116 Catal. Surv. Asia 14 Green Chem 5 Polymer 54 J. Appl. Polym. Sci 63 8 JSR TECHNICAL REVIEW No.123/2016