Five-membered Cyclic Dithiocarbonate Research Articles

A strategy combining quantitative reactions and reversible-covalent chemistry for sequential synthesis of sequence-controlled polymers with different sequences

A new strategy combing quantitative reactions and reversible-covalent chemistry is proposed for sequential synthesis of a series of sequence-controlled polymers with different sequences. Using a Michael addition reaction between acrylate and thiol, an aminolysis reaction of five-membered cyclic dithiocarbonate and a thiol substitution reaction of bromomaleimide and thiol, AB-, AB'C- and AB'CD-sequenced molecules are synthesized via AB, AB'C and AB'CD sequential monomer additions, respectively. These three molecules all have furan-protected maleimido group at one end, and the other end of AB-, AB'C- and AB'CD-sequenced molecules is amine, thiol and anthracene groups, respectively. Due to the fact that the furan-protected maleimido group can be efficiently transformed to maleimide group at high temperature via retro Diels-Alder reaction, AB-, AB'C- and AB'CD-sequenced molecules polymerize into sequence-controlled polymers with corresponding sequences at 120 °C. Through this strategy, the synthesis of molecular modules does not require separation and purification, and sequence-controlled polymers with specific sequence can be synthesized in a one-pot process via adding different monomers and adjusting reaction condition.

Radical Copolymerization of Methacrylate Bearing Five-Membered Cyclic Dithiocarbonate Moiety and 2-Hydroxyethyl Methacrylate and Its Application to Networked Polymer Synthesis

Radical Copolymerization of Methacrylate Bearing Five-Membered Cyclic Dithiocarbonate Moiety and 2-Hydroxyethyl Methacrylate and Its Application to Networked Polymer Synthesis

Synthesis and properties of poly(thiourethane)s having soft oligoether segments

Polyaddition of bis(five-membered cyclic dithiocarbonate), 2,2-bis[4-(1,3-thioxolane-2-one-4-yl-methoxy)phenyl]propane (1), with diamines having soft oligoether segments and property of the obtained poly(thiourethane)s were examined. Treatment of 1 with equivalent diamines in tetrahydrofuran at room temperature gave poly(thiourethane)s having a mercapto group in each unit, which were further treated with acetic anhydride and triethylamine to give the corresponding S-acetylated poly(thiourethane)s in high yield. Exposing the mercapto group containing poly(thiourethane)s to benzoyl chloride and triethylamine provided the corresponding S-benzoylated poly(thiourethane)s effectively. Thermal properties of the obtained polymers were evaluated by thermogravimetric analysis and differential scanning calorimetry. The obtained polymers showed 10 wt % loss temperature (Td10) in the range from 230 to 274 °C, which was relatively high when compared with the Td10 of an analogous polymer prepared from 1 and 1,6-hexamethylenediamine. The polymers obtained here exhibited glass transition temperature (Tg) in the range from −16 °C to 40 °C, which was much lower than the analogous polymer described above, probably due to the soft oligoether segments. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 1076–1081

Synthesis of graft terpolymers by addition reaction of amino-terminated polyether to poly(methacrylate)s bearing five-membered cyclic dithiocarbonate moieties and application of the graft terpolymers as modifiers for wool

Graft terpolymers bearing polyether side chains and poly(methacrylate) stems were synthesized by the graft-onto reaction of monoamino-terminated poly(PO9-co-EO1) to poly{[5-(methacryloyloxy)methyl-1,3-oxathiolane-2-thione]-co-n-butyl methacrylate} [poly(DTCMMA-co-BuMA)]. The grafting reaction proceeded via the nucleophilic addition of the terminal amino groups to the five-membered cyclic dithiocarbonate moieties giving thiol moieties, although the grafting efficiency was low (9–34%) due to the steric hindrance of the side chains. The Tg values of the poly{[DTCMMA-graft-poly(PO9-co-EO1)]-co-BuMA} ranged 27–47 °C, depending on the amounts of flexible poly(PO9-co-EO1) chains introduced lowering the Tg values. Poly{[DTCMMA-graft-poly(PO9-co-EO1)]-co-BuMA}s bearing thiol groups were applied for the modification of wool via the disulfide exchange reaction. The modified wool had better dye ability toward a pigment from safflower than the original wool owing to the hydrophilic nature of poly{[DTCMMA-graft-poly(PO9-co-EO1)]-co-BuMA} introduced. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Synthesis of refractive star-shaped polysulfide by anionic polymerization of phenoxy propylene sulfide using an initiating system consisting of trifunctional thiol derived from five-membered cyclic dithiocarbonate and amine

Star-shaped poly(phenoxy propylene sulfide) [poly (PPS)] were synthesized by anionic polymerization using a trifunctional initiator (I 1 ) derived from a trifunctional five-membered cyclic dithiocarbonate and benzyl amine. Conditions for the anionic polymerization of PPS were optimized to obtain polymers with desired M n s and narrow M w /M n s. The best catalyst and solvent were DBU and DMF, respectively. The star-shaped structure of the resulting star poly(PPS) was supported by SEC analysis. The refractive indexes (n D ) of the star poly (PPS) were relatively high (>1.64).

Efficient Chemical Recycling System of Networked Polymer: De-Cross-Linking of Cross-Linked Polymer Obtained from Bis(five-membered cyclic dithiocarbonate)

Efficient Chemical Recycling System of Networked Polymer: De-Cross-Linking of Cross-Linked Polymer Obtained from Bis(five-membered cyclic dithiocarbonate)

Star-Shaped Polymer Synthesis by Anionic Polymerization of Propylene Sulfide Based on Trifunctional Initiator Derived from Trifunctional Five-Membered Cyclic Dithiocarbonate

Star-Shaped Polymer Synthesis by Anionic Polymerization of Propylene Sulfide Based on Trifunctional Initiator Derived from Trifunctional Five-Membered Cyclic Dithiocarbonate

Living ring-opening polymerization based on neighboring group participation

Cationic ring-opening polymerization of a five-membered cyclic dithiocarbonate having benzoxymethyl group; 5-benzoxymethyl-1,3-oxathiolane-2-thione, was carried out with TfOH or TfOMe as an initiator in PhCl at rt – 60 °C. The molecular weight distribution (Mw/Mn) of the polymer obtained with TfOMe was very narrow even at 60 °C (Mw/Mn 1.14), and the Mn value of the polymers estimated by GPC was in good agreement with the molecular weight determined from ¹H-NMR. The living nature of the polymerization was confirmed by the conversion dependence of the Mn (Mw/Mn) and the correlation of the experimental and theoretical Mn (Mw/Mn) values.

A Novel Construction of Living Polymerization by Neighboring Group Participation: Living Cationic Ring-Opening Polymerization of a Five-Membered Cyclic Dithiocarbonate

A Novel Construction of Living Polymerization by Neighboring Group Participation: Living Cationic Ring-Opening Polymerization of a Five-Membered Cyclic Dithiocarbonate

Novel one-pot polymer syntheses based on dithiols obtained from a five-membered cyclic dithiocarbonate and diamines

Novel one-pot syntheses of sulfur-containing polymers from a five-membered cyclic dithiocarbonate (5-phenoxymethyl-1,3-oxathiolane-2-thione (1)) and diamines were examined. Polydisulfides with M̄n 5400 ∼ 15800 were obtained in the oxidation polymerization of dithiols 2, which were obtained in situ by the reactions of 1 and diamines. When 1,12-dodecanediamine was employed, a polydisulfide with relatively high M̄n was obtained, while in the case of m-xylylenediamine, the polymerization was accompanied by intermolecular cyclization to give a polydisulfide with low M̄n. Polythiourethanes with M̄n 6500 ∼ 17200 were obtained in the polyaddition of 2 with 4,4′-methylenebis(phenyl isocyanate). The yields and M̄n values increase with increasing methylene chain length of 2. Polythioethers with M̄n 2600 ∼ 19900 were obtained by the polycondensations of 2 with α,α′-dibromo-p-xylene. The glass transition temperature (Tg) of the polymer decreases with increasing methylene chain length in the main chain.

Novel one-pot polymer syntheses based on dithiols obtained from a five-membered cyclic dithiocarbonate and diamines

Novel one-pot syntheses of sulfur-containing polymers from a five-membered cyclic dithiocarbonate (5-phenoxymethyl-1,3.-oxathiolane-2-thione (1)) and diamines were examined. Polydisulfides with M n 5400∼15800 were obtained in the oxidation polymerizations of dithiols 2, which were obtained in situ by the reactions of 1 and diamines. When 1,12-dodecanediamine was employed, a polydisulfide with relatively high M n was obtained, while in the case of m-xylylenediamine, the polymerization was accompanied by intermolecular cyclization to give a polydisulfide with low M n . Polythiourethanes with M n 6500∼17200 were obtained in the polyaddition of 2 with 4,4'-methylenebis(phenyl isocyanate). The yields and M n values increase with increasing methylene chain length of 2. Polythioethers with M n 2600∼19900 were obtained by the polycondensations of 2 with a,a'-dibromo-p-xylene. The glass transition temperature (T g ) of the polymer decreases with increasing methylene chain length in the main chain.

Novel one-pot polymer syntheses based on dithiols obtained from a five-membered cyclic dithiocarbonate and diamines

Novel one-pot polymer syntheses based on dithiols obtained from a five-membered cyclic dithiocarbonate and diamines

Novel one-pot syntheses of sulfur-containing polymers from a bifunctional five-membered cyclic dithiocarbonate

Novel one-pot syntheses of sulfur-containing polymers from a bifunctional five-membered cyclic dithiocarbonate (1a) were carried out. Polythiourethanes were obtained by the polyaddition of 4,4′-methylenebis(phenyl isocyanate), tolylene 2,6-diisocyanate, and hexamethylene diisocyanate with a dithiol (2a) obtained by the reaction of 1a and benzylamine under mild conditions. Polythioesters were also obtained by the polycondensation of terephthaloyl and succinyl chlorides with 2a. Further, polythioether was obtained by the polycondensation of α,α′-dibromo-p-xylene with 2a. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1189–1195, 1998