Polyaddition Of Bis Research Articles

Protecting-group-free synthesis of functional Poly(ester amide)s by the polyaddition of Bis(aziridine)s

The protecting-group-free synthesis of reactive functional group containing poly(ester amide)s (PEAs) is reported. The synthesis of the PEAs is based on the nucleophilic ring-opening polyaddition of terephthalaziridine (TP-Az) with comonomers baring carboxylic acid and phenols as nucleophiles. The comonomers also contained the reactive functional groups aldehyde, ketone, ester, alcohol, furan, disulfide and siloxane, which were incorporated into the resulting PEAs without any detectable side reactions. A multicomponent polymerization was conducted to further demonstrate the versatility of this method. These PEAs are amorphous with high thermal stability (Td,5 %: 231–324 °C) and a have wide range of glass transition temperatures (Tg) (32–142 °C). The disulfide and siloxane-containing copolymers PEAs selectively degrade in the presence of dithiothreitol and fluoride respectively. The PEAs also underwent alkaline hydrolysis to yield a potential TP-Az, potentially facilitating chemical recycling of these PEAs.

Synthesis of non-isocyanate poly(hydroxyurethane)s (NI-PHUs) using diglycidyl ethers

In this study, we synthesized non-isocyanate poly(hydroxyurethane)s (NI-PHUs) via the polyaddition of bis(cyclic carbonate)s and diamines. Bis(cyclic carbonate)s were prepared by reacting resorcinol diglycidyl ether and neopentyl glycol diglycidyl ether with CO2. NI-PHUs were obtained through the reaction of the bis(cyclic carbonate)s with either an aliphatic or a cycloaliphatic diamine. The identities of the synthesized products were confirmed via 1H NMR and FT-IR spectroscopy. The glass transition temperatures (Tgs) of the NI-PHUs were higher when resorcinol diglycidyl ether was used to synthesize the bis(cyclic carbonate) instead of neopentyl glycol diglycidyl ether. The NI-PHUs prepared with isophorone diamine had significantly higher Tgs than those prepared with 1,4-diaminobutane.

Renewable natural resources as green alternative substrates to obtain bio-based non-isocyanate polyurethanes-review

Commercially available polyurethanes are synthesized by the polyaddition of diisocyanates with polyols and low molecular weight chain extenders. A new approach to polyurethanes synthesis is realized via non-isocyanate routes. Negative impacts of petroleum-based chemicals on the environment and human health as well as gradual reduction of fuel-based resources, which leads to an increase in their prices, are an incentive to looking for bio-based components derived from renewable resources for the polyurethanes synthesis. The purpose of the presented review is a critical summary of the possibilities of using renewable natural resources as green intermediates to obtain non-isocyanate polyurethanes by polyaddition of bis(cyclic carbonate)s and di- or polyamines. The possibility of using carbon dioxide, plant oils, fatty acids and biomass-derived platform chemicals in non-isocyanate polyurethane synthesis is exhaustively commented.

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

Furan-based polysemiacylcarbazides by polyaddition of bis(furanic hydrazide)s with diisocyanates

A solution polyaddition procedure was applied to prepare furanic polyacylsemicarbazides based on 2,2′-isopropylidene-bis(5-(2-furoyl) hydrazide) and aliphatic or aromatic diisocyanates. Model compo...

Furan-based Polysemiacylcarbazides by Polyaddition of Bis(furanic hydrazide)s with Diisocyanates

A solution polyaddition procedure was applied to prepare furanic polyacylsemicarbazides based on 2,2′-isopropylidene-bis(5-(2-furoyl) hydrazide) and aliphatic or aromatic diisocyanates. Model compounds were prepared to facilitate the synthesis and the characterization of the polymers. A systematic study of reaction parameters (the nature of the organic phase, the temperature, the reaction time, and the concentration of monomers) was carried out. High MW polymers were obtained after 12 h reaction at 20°C with 0.2 M monomer solutions in dimethylacetamide. In fact, the polyacylsemicarbazides obtained had inherent viscosities ranging from 0.63 to 0.85 dL/g. There showed good solubility in aprotic polar solvents. The 1H and 13C-NMR spectra were consistent with the expected structures. These furan-based polyacylsemicarbazides are thermally stable up to 290°C, but exhibit a complex thermal behavior. This was explained by the cyclohydration of acylsemicarbazide groups into NH-substituted oxadiazoles, resulting in rigid and high melting polymers, less stable, however, than conventional aromatic polyoxadiazoles.

Synthesis and characterization of functional polyesters tailored for biomedical applications

AbstractThis work aimed at the development of bioactive polymeric materials to be used for targeted drug delivery and tissue engineering applications. The proposed strategy was based on the design of macromolecular systems whose functionality can be easily modified. Polyesters containing side‐chain end capped by primary hydroxyl groups were synthesized by polyaddition of oxetanes and carboxylic anhydrides catalyzed by quaternary onium salts. The polyaddition of bis(oxetane) with different dicarboxylic acids was also investigated. In all cases, oxetane monomers contained one hydroxyl group either free or protected by a benzyl group. The polymer yield and molecular weight were relatively high when aromatic anhydrides were used. In all other cases, low conversions or no polymerization at all were obtained. In a parallel research line, several alkanols were successfully employed to synthesize different α,β′,β‐trisubstituted‐β‐lactones. These monomers were prepared in five steps starting from diethyl oxalpropionate according to established synthetic routes. Final yields depended on both preparation method and side‐chain structure. By using quaternary ammonium salts as catalysts, the synthesized functional lactones underwent anionic ring opening polymerization leading to the corresponding homopolymers and copolymers in fairly good yields. The prepared polymeric materials were extensively characterized by spectroscopic techniques, size exclusion chromatography, and thermal analysis. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2459–2476, 2008

Synthesis and refractive‐index control of fluoropolymers by the polyaddition of bis(epoxide)s and triazine di(aryl ether)s

AbstractThe polyaddition of fluorine‐containing bis(epoxide)s and fluorine‐containing triazine di(aryl ether)s were examined to give the corresponding fluorine‐containing poly(cyanurate)s. It was observed that the synthesized fluoropolymers had good thermal stabilities and good film‐forming properties. The glass transition temperatures (Tg's) and refractive‐indices (nD's) of synthesized polymers were determined by differential scanning calorimetry and ellipsometry, respectively, and it was found that the values of Tg's and nD's were supported by their fluorine containing ratios and skeletons. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4421–4429, 2007

Catalytic reactions of oxetanes with protonic reagents and aprotic reagents leading to novel polymers

AbstractThis paper reports new addition reactions of oxetanes with certain protonic reagents such as carboxylic acid, phenol, and thiol, and with certain aprotic reagents such as acyl chloride, thioester, phosphonyl dichloride, silyl chloride, and chloroformate using quaternary onium salts as catalysts. The kinetic study of the addition reactions of oxetanes was also investigated. These new addition reactions were applicable to the synthesis of new polymers. These polyaddition systems could also construct both polymer main chains and reactive side chains. The alternating copolymerization of oxetanes with carboxylic anhydride was performed. Furthermore, it was found that anionic ring‐opening polymerization of oxetanes containing hydroxy groups proceeded to afford the hyperbranched polymer (HBP) with an oxetanyl group and many hydroxy groups at the ends of the polymer chains. Alkali developable photofunctional HBPs were synthesized by the polyaddition of bis(oxetane)s or tris(oxetane)s, and their patterning properties were examined, too. The photo‐induced cationic polymerization of the polymers with pendant oxetanyl groups and the thermal curing reactions of polyfunctional oxetanes (oxetane resins) were also examined to give the crosslinking materials quantitatively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 709–726, 2007

Synthesis of Hyperbranched Poly(ester)s with Pendant Hydroxy Groups by the Polyaddition of Bis(oxetane)s with 1,3,5-Benzenetricarboxylic Acid

Synthesis of Hyperbranched Poly(ester)s with Pendant Hydroxy Groups by the Polyaddition of Bis(oxetane)s with 1,3,5-Benzenetricarboxylic Acid

オキセタン化合物の新規開環反応による構造制御された高分子の合成

This article reports new ring-opening reactions of oxetane compounds with certain reagents such as acyl chlorides, carboxylic esters, phenols, and carboxylic acids using certain quaternary onium salts as catalysts. Reaction behavior of oxetanes was investigated based on kinetic study. These new reactions of oxetanes were also successfully applied to polymer synthesis. Polymers containing pendant reactive groups were obtained by polyaddition of bis (oxetane) s with certain difunctional monomers such as dicarboxylic chlorides, bis (phenol) s, or dicarboxylic acids. The reaction of oxetanes with cyclic carboxylic anhydrides proceeded in alternating ring-opening copolymerization mode to give copolymers with A-B sequence. The authors found new anionic ring-opening polymerization of oxetanes containing pendant hydroxyl groups using appropriate catalyst system. Hyperbranched polymers containing hydroxyl groups were prepared by the reactions of oxetanes. Alkali developable photopolymers were also obtained by the chemical modification of the hyperbranched polymers. The reactions of oxetanes with certain reagents were also useful for thermal curing reaction providing oxetane resins.

Synthesis of Poly(ether)s with Pendant Ester Groups by the Polyaddition of Bis(oxetane)s with Active Bis(ester)s

Synthesis of Poly(ether)s with Pendant Ester Groups by the Polyaddition of Bis(oxetane)s with Active Bis(ester)s

Synthesis and properties of fluorine‐containing polyethers with pendant hydroxyl groups by the polyaddition of bis(epoxide)s with diols

AbstractFluorine‐containing polyethers with pendant hydroxyl groups were synthesized by the polyaddition of fluorine‐containing bis(epoxide)s with certain fluorine‐containing diols with quaternary onium salts as catalysts. When the polyaddition was performed with 2,2′,6,6′‐tetrafluoro‐4,4′‐biphenol diglycidiyl ether and 2,2′,6,6′‐tetrafluoro‐4,4′‐biphenol, the corresponding polyether with pendant hydroxyl groups was successfully obtained in good yield. The polyaddition of certain fluorine‐containing bis(epoxide)s with diols also proceeded in bulk to provide the corresponding fluorine‐containing polyethers with high molecular weights. These polyethers were highly transparent at 157 nm for 0.1 μm thickness, with their transmittance of 14–75% at 157 nm. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2543–2550, 2004

Synthesis of polyesters by the polyaddition of bis(oxetane)s with active di(ester)s

AbstractThe polyaddition of bis(oxetane)s 1,4‐bis[(3‐ethyl‐3‐oxetanylmethoxymethyl)]benzene (BEOB), 4,4′‐bis[(3‐ethyl‐3‐oxetanyl)methoxy]benzene (4,4′‐BEOBP), 1,4‐bis[(3‐ethy‐3‐oxetanyl)methoxy] ‐benzene (1,4‐BEOMB), 1,2‐bis[(3‐ethyl‐3‐oxetanyl)methoxy]benzene (1,2‐BEOMB), 4,4‐bis[(3‐ethyl‐3‐oxetanyl)methoxy]biphenyl (4,4′‐BEOMB), 3,3′,5,5′‐tetramethyl‐[4,4′‐bis(3‐ethyl‐3‐oxetanyl)methoxy]biphenyl (TM‐BEOBP) with active diesters di‐s‐phenylthioterephthalate (PTTP), di‐s‐phenylthioisoterephthalate (PTIP), 4,4′‐di(p‐nitrophenyl)terephthalate (NPTP), 4,4′‐di(p‐nitrophenyl)isoterephthalate (NPIP) were carried out in the presence of tetraphenylphosphonium chloride (TPPC) as a catalyst in NMP for 24 h, affording corresponding polyesters with Mn's in the range 2200–18,200 in 41–98% yields. The obtained polymers would soluble in common organic solvents and had high thermal stabilities. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1528–1536, 2004

Synthesis and Properties of Fluorine-containing Poly(ether)s with Pendant Hydroxyl Groups by the Polyaddition of Bis(oxetane)s and Bisphenol AF

Fluorine-containing poly(ether)s with pendant primary hydroxyl groups were synthesized by the polyaddition of bisphenol AF di(3-ethyl-3-oxetanylmethyl ether) (BPAFEO) with bisphenol AF (BPAF) using quaternary onium salts, crown ether complexes or organic bases as catalysts. When the polyaddition was performed with co-catalysts such as tetraphenylphosphonium chloride (TPPC) and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) without solvent at 190 °C for 120 h, the corresponding poly(ether)s pendant primary hydroxyl groups were successfully obtained in good yield. The polyaddition of various bis(oxetane)s with BPAF also proceeded in bulk to provide the corresponding poly(ether)s. It was found that these poly(ether)s are highly transparent at 157 nm, and transmittance of poly(ether)s were determined to be 34–55 % at 157 nm for 0.1 μm thickness.

Novel synthesis of reactive polycarbonates with pendant chloromethyl groups by the polyaddition of bis(oxetane)s with 2,2′‐bis[(4‐chloroformyl)oxyphenyl]propane

AbstractThe polyaddition of 1,4‐bis[(3‐ethyl‐3‐oxetanyl)methoxymethyl]benzene with 2,2′‐bis[(4‐chloroformyl)oxyphenyl]propane was examined with quaternary onium salts as catalysts. When the polyaddition was carried out with tetrabutylphosphonium bromide in chlorobenzene at 120 °C for 24 h, the corresponding poly(alkyl aryl carbonate) with a high molecular weight (number‐average molecular weight = 16,700) was obtained in an almost quantitative yield. It was found from the 1H NMR and 13C NMR spectra of the obtained polymer that the addition reaction proceeded without any side reactions, providing the polycarbonate with pendant chloromethyl groups in the side chain. The polyaddition of bis{[3‐(3‐ethyloxetanyl)]methyl}terephthalate also proceeded smoothly and gave the corresponding polycarbonate with high molecular weight in a good yield. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2304–2311, 2003

Synthesis and characterization of fluorine‐containing polyesters by the polyaddition of bis(epoxide)s with active diesters

AbstractThe synthesis and optical properties of polyesters with pendant fluorinated phenoxy groups were examined. The polyaddition of bisphenol AF diglycidyl ether (1) with fluorine‐containing terephtalates (2a–f) was carried out with tetrabutylphosphonium chloride (TBPC) as the catalyst in chlorobenzene to afford the corresponding polyesters with number‐average molecular weights (Mn's) ranging from 15,200 to 30,000 in 88–96% yields. Furthermore, the polyaddition of 1 with isophthalate 2g and phthalate 2h also produced high‐molecular‐weight polyesters with Mn's = 22,700 and 22,600 in 88 and 84% yields, respectively. The linear relationship was observed between the fluorine contents and refractive indices of the obtained polyesters. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 213–222, 2003

Synthesis of polyphosphonates containing pendant chloromethyl groups by the polyaddition of bis(oxetane)s with phosphonic dichlorides

AbstractThe polyaddition of 4,4′‐bis[(3‐ethyl‐3‐oxetanyl)methoxy]biphenyl (4,4′‐BEOBP) and phenylphosphonic dichloride (PPDC) with quaternary onium salts as catalysts proceeded under mild reaction conditions to afford a polymer containing phosphorous atoms in its main chain. A polyphosphonate with a high number‐average molecular weight (10,300) was obtained by the reaction of 4,4′‐BEOBP and PPDC in the presence of tetraphenylphosphonium chloride (TPPC) in o‐dichlorobenzene at 130 °C for 24 h. The structure of the resulting polymer was confirmed with IR, 1H NMR, and 31P NMR spectroscopy. Furthermore, it was proved that the polyaddition of certain bis(oxetane)s with phosphonic dichlorides proceeded smoothly to give corresponding polyphosphonates with TPPC as the catalyst. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3835–3846, 2002

Synthesis and characterization of fluoropolymers by the polyaddition of bis(epoxide)s with dicarboxylic acids and diols

AbstractThe synthesis and characterization of the fluoropolymers poly1a–1d and poly2a–2d with pendant hydroxyl groups were examined. The polyaddition of bis(epoxide)s [2,2′‐bis(4‐glycidyletherphenyl)hexafluoropropane and bisphenol A diglycidyl ether] with dicarboxylic acids (tetrafluoroterephthalic acid and terephthalic acid) and diols [2,2′‐bis(4‐hydroxyphenyl)hexafluoropropane, 2,2′,3,3′,5,5′,6,6′‐octafluoro‐4,4′‐biphenol, 1,4‐bis(hexafluorohydroxyisopropyl)benzene, and 1,3‐bis(hexafluorohydroxyisopropyl)benzene] was carried out at 50–100 °C for 6–48 h in the presence of quaternary onium salts (tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylphosphonium bromide, and tetrabutylphosphonium chloride; 2.5 mol %) as catalysts in dimethyl sulfoxide, N‐methylpyrrolidone, dimethylformamide, dimethylacetamide, dioxane, diglyme, o‐dichlorobenzene, chlorobenzene, and toluene to afford the corresponding polymers, poly1a–1d and poly2a–2d, with number‐average molecular weights of 11,000–59,400 in 45–97% yields. The solubility of the obtained polymers was good, and their thermal stability might be assumed from their structures. A linear relationship was observed between the contents of the fluorine atoms and the refractive indices. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1395–1404, 2002

Polyaddition of bis(seven‐membered cyclic carbonate) with diamines: A novel and efficient synthetic method for polyhydroxyurethanes

AbstractThis article deals with the polyaddition of a novel bis(seven‐membered cyclic carbonate), 1,2‐bis[3‐(1,3‐dioxepan‐2‐one‐5‐yl)‐propylthio]ethane, with the diamines 4,9‐dioxa‐1,12‐dodecanediamine and p‐xylylenediamine. The polyaddition was carried out at 30–70 °C for 6–24 h in dimethyl sulfoxide to obtain the corresponding polyhydroxyurethanes with number‐average molecular weights of 10,900–35,700 in good yields. The reaction of a monofunctional seven‐membered cyclic carbonate, 5‐allyl‐1,3‐dioxepan‐2‐one (7CC), with monoamines was also carried out to examine the reactivity in comparison with that of six‐ and five‐membered cyclic carbonates. The reaction rate constants of 7CC with n‐hexylamine and benzylamine were estimated to be 48.5 and 11.0 L/mol · h, respectively, in dimethyl sulfoxide‐d6 (initial reagent concentration = 1 M) at 30 °C. The seven‐membered cyclic carbonate ring was 2.98 and 5.82 kcal/mol more strained than those of the six‐ and five‐membered cyclic carbonates, respectively, according to a semiempirical molecular orbital calculation with the PM3 Hamiltonian. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4091–4100, 2001