Mono‐ and bifunctional six‐membered cyclic carbonates synthesized by diphenyl carbonate toward networked polycarbonate films

2015

RSC Adv.

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Polyhydroxyurethanes (PHUs) are synthesized by the polyaddition of di(trimethylolpropane) carbonate (DTMPC) and a series of conventional aliphatic diamines, and are then chemically modified through their side chains to design quaternary ammonium chloride (QAC)-functionalized PHU films. The reaction of DTMPC with a subtle excess of diamines affords PHUs with well-controlled molecular weights and polydispersities. The hydroxyl groups of these PHUs are modified with chloroacetyl chloride and then reacted with N,N-dimethyl-n-octylamine (DMOA) to easily give QAC-functionalized PHUs. On the other hand, the reaction of these PHUs with cross-linkable N,N,N 0 ,N 0 -tetramethyl-1,6-diaminohexane (TMDAH) undergoes quaternization and simultaneously forms networked structures, resulting in the formation of QAC-functionalized PHU network films. In particular, the use of 20 mol% TMDAH, with respect to the chloroacetyl groups of the PHU unit, gives a self-supported film with a good transparency and higher thermal stability. Furthermore, the remaining chloroacetyl groups of the film can be modified with DMOA to afford PHU films with dual-structured QAC moieties. The resulting PHU film constructs positively charged surfaces with a zeta potential of +8.3 mV.

Section: Resultsmentioning

confidence: 99%

“…50 A series of aliphatic diamines was purchased from Tokyo Chemical Industry Co., Ltd and Aldrich Co., Ltd and used without any purication. 50 A series of aliphatic diamines was purchased from Tokyo Chemical Industry Co., Ltd and Aldrich Co., Ltd and used without any purication.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of polyhydroxyurethanes from di(trimethylolpropane) and their application to quaternary ammonium chloride-functionalized films

2015

RSC Adv.

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“…S14) and rather resembled that of networked polycarbonate film which had been prepared without ethanol amine derivatives (Supporting Information Fig. S20) . Therefore, the changes in the thermal stability would be due to the formation of networked structures based on DTMPC.…”

Section: Resultsmentioning

confidence: 99%

“…S20). 22 Therefore, the changes in the thermal stability would be due to the formation of networked structures based on DTMPC. TGA profiles for other three films were roughly same as that of Film A but the order in which the thermal decomposition occurred was accorded with that of the non-networked polycarbonates (Supporting Information Fig.…”

Section: Fabrication Of Tertiary Amine-modified Polycarbonate Filmsmentioning

confidence: 99%

“…Such networks are easily formed by the copolymerization of mono‐ and bifunctional carbonates bearing six‐membered cyclic structures. Recently, we have reported the facile synthetic route to six‐membered cyclic carbonates through the transesterification with diphenyl carbonate (DPC) instead of conventional phosgene derivatives . Compared to dimethyl carbonate or diethyl carbonate, DPC features a higher reactivity originating from its leaving group (phenolate ion), and therefore, the transesterification of neopentylglycol (NPG) or di(trimethylolpropane) (DTMP) can afford the corresponding neopentylglycol carbonate (NPGC) or di(trimethylolpropane) carbonate (DTMPC) in high yields.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Ring-opening polymerization of six-membered cyclic carbonates initiated by ethanol amine derivatives and their application to protonated or quaternary ammonium salt-functionalized polycarbonate films

J. Polym. Sci. Part A: Polym. Chem.

2015

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Ring-opening polymerization (ROP) of monofunctional neopentylglycol carbonate (NPGC) with or without bifunctional di(trimethylolpropane) carbonate (DTMPC), which are derived from available corresponding alcohols, affords linear polycarbonates or covalently-linked polycarbonate networks, respectively. A series of available ethanol amine derivatives having the different numbers of 2-hydroxylethyl arms (N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine, triethanolamine, N-methyldiethanolamine or N,N-dimethylethanolamine) initiates the ROP of NPGC to afford star-shaped, telechelic, or linear polycarbonates bearing tertiary amines with well-controlled molecular weights and relatively narrow polydispersities Furthermore, the copolymerization of NPGC and DTMPC in the presence of these initiators readily gives tertiary amine-modified polycarbonate films with well transparency and flexibility. These amino groups are easily converted to ammonium salts by protonation with acids, while the quaternization with benzyl bromide is strongly affected by the steric hindrance of these amines. N-Methyldiethanolamine or N,N-dimethylethanolamine residues in these films react easily with benzyl bromide to give quaternary ammonium saltfunctionalized films.

Phosgene‐Free Syntheses and Hydrolytic Properties of Water‐Soluble Polyhydroxyurethanes with Ester–Carbonate–Ether Structures in Their Main Chains

Macro Chemistry & Physics

2017

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Three types of bifunctional 6-membered cyclic carbonates bearing ester, acyclic carbonate or ether moieties have been derived from nonexpensive trimethylolpropane or di(trimethylolpropane) through phosgene-free routes and used for the polyaddition reaction with 1,3-diaminopropane to design polyhydroxyurethanes (PHUs) containing the corresponding linkages in their main chains. Furthermore, these PHUs have been chemically modified via their OH groups to afford water-soluble PHUs (WSPHUs) and characterized for their hydrolytic properties at different pH conditions. Carbonate and ester bonds in these WSPHUs are easily hydrolyzed under basic conditions and their hydrolytic rates depend on their main chain structures; WSPHUs bearing carbonate structures are degraded faster than WSPHUs with ester linkages, while WSPHUs having ether bonds are slowest hydrolyzed. Moreover, the hydrolytic rates of these WSPHUs can be modulated by the copolymerization of these monomers at different feed ratios.