FREE RADICAL RING OPENING POLYMERIZATION OF CYCLIC ACRYLATES

Cyclic acrylates, 2,2- dimethyl-5-methylene-1 , 3-dioxolan-4 -one and 2- phenyl-5-methylene-1,3-dioxolan-4-one, were synthesized successfully. The monomers were characterized by ~1H NMR, ~(13)C NMR, IR and elemental analysis or HRMS. Polymerization of the monomers were carried out at 120℃with di-t-butylperoxide as initiator. The polymers were studied by ~1H NMR, ~(13)C NMR, UV and hydrolysis. The molecular weights of the resulting polymers were estimated by viscosity measurement and the extent of ring opening was estimated also by ~1H NMR and hydrolysis of the polymers and further confirmed by UV spectra.     

Synthesis and stability study of dental monomers containing methacrylamidoethyl phosphonic acids

Three new dental monomers containing methacrylamidoethyl phosphonic acids were synthesized. The structures of the synthesized monomers were determined with electrospray mass spectrometry (ESMS), Fourier transform infrared, and NMR. The hydrolytic stabilities of the synthesized monomers and a commercial monomer, 2‐methacryloyloxyethyl phosphoric acid (MEP; used as a control), were studied with flow injection (FI)/ESMS, ¹H NMR, and ³¹P NMR analysis of a CD₃OD/D₂O (4:1 v/v) solution of each monomer before and after storage at 60 °C for 2 months. The ¹H NMR and ³¹P NMR chemical shifts of the monomers 2‐methacrylamidoethylphosphonic acid ( I ) and N,N′‐[4,4′‐(propane‐2,2‐diyl)‐bis(phenoxy‐2‐hydroxypropyl)]‐bis(2‐methacrylamidoethylphosphonic acid) ( II ) showed little change after storage at 60 °C for 2 months, but those of MEP changed significantly. FI/ESMS also showed that MEP was nearly completely decomposed, whereas monomers I and II remained largely intact. MEP could react with H₂ZrF₆ to form ternary zirconium fluoride complexes that were partially soluble in methanol, but all the monomers containing phosphonic acids formed precipitates. This study demonstrates that ESMS is a more sensitive and effective method than NMR for studying the hydrolytic stability or degradation of dental monomers. The new monomers containing methacrylamidoethyl phosphonic acids have higher hydrolytic stability than methacrylate phosphate monomers and may be used in dental bonding agents and other dental materials. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 99–110, 2007     

Gradient copolymers of ε-caprolactone and δ-valerolactone via solvent-free ring-opening copolymerization with a pyridyl-urea/MTBD system

The ring-opening copolymerization of ε-caprolactone and δ-valerolactone was carried out under solvent-free conditions with a pyridyl-urea ( 6C-PU )/7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene catalytic system by premixing two monomers, yielding gradient copolyesters with cyclic and linear structures in the absence or presence of an initiator, respectively. The random and block copolyesters of these two monomers were also prepared for comparison. The results of ¹H and ¹³C NMR spectra determined the linear and cyclic structure of copolymers. The kinetic experiment was used to determine the consuming rates of two monomers during the polymerization. The topologies and thermal properties of all the copolymers were characterized and compared by NMR and DSC.     

Synthesis and evaluation of new dental monomers with both phosphonic and carboxylic acid functional groups

Novel dental monomers containing both phosphonic and carboxylic acid functional groups were prepared. The monomers were based on t‐butyl α‐bromomethacrylate (t‐BuBMA) and synthesized in three steps: The reaction of o‐hydroxyaryl phosphonates [diethyl (2‐hydroxyphenyl) phosphonate, tetraethyl (2,5‐dihydroxy‐1,4‐phenylene) diphosphonate and tetraethyl 5,5′‐(propane‐2,2‐diyl)bis(2‐hydroxy‐5,1‐ phenylene) diphosphonate] with t‐BuBMA, the hydrolysis of phosphonate groups to phosphonic acid using trimethyl silylbromide, and the hydrolysis of the t‐butyl groups to carboxylic acid with trifluoroacetic acid. The monomers were solids and soluble in water and ethanol. The structures of the monomers were determined by Fourier transform infrared (FTIR), ¹H, ¹³C, and ³¹P nuclear magnetic resonance (NMR) spectroscopy. The copolymerization behaviors of the synthesized monomers with glycerol dimethacrylate were first investigated in bulk using photodifferential scanning calorimetry at 40 °C with 2,2′‐dimethoxy‐2‐phenyl acetophenone as photoinitiator. Then, the solution copolymerization of the monomers with acrylamide in ethanol and water was studied, indicating that the synthesized monomers are incorporated into the copolymers. The acidic nature of the aqueous solutions of these monomers (pH values 1.72–1.87) is expected to give them etching properties important for dental applications. The interaction of the monomers with hydroxyapatite was investigated using ¹³C NMR and FTIR techniques. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1953–1965, 2009     

Polymerisation of cyclic monomers, 8. Synthesis and radical polymerisation of hybrid 2‐vinylcyclopropanes

Hybrid 2‐vinylcyclopropanes were synthesised by the esterification of 1‐methoxycarbonyl‐2‐vinylcyclopropane‐1‐carboxylic acid with hydroxy group containing (meth)acrylates in the presence of 1,3‐dicyclohexylcarbodiimide (DCC). The structure of the new hybrid monomers was confirmed by elemental analysis, IR, ¹H NMR and ¹³C NMR spectroscopy. The radical polymerisation of the hybrid monomers in bulk with 2,2'‐azoisobutyronitrile (AIBN) results in transparent cross‐linked polymers, whereas solution polymerisation partially results in soluble polymers with pendant 2‐vinylcyclopropyl groups.     

Synthesis,photopolymerization and adhesive properties of new hydrolytically stable phosphonic acids for dental applications

Novel monomers 2‐(N‐methylacrylamido)ethylphosphonic acid, 6‐(N‐methylacrylamido)hexylphosphonic acid, 10‐(N‐methylacrylamido)decylphosphonic acid, and 4‐(N‐methylacrylamidomethyl)benzylphosphonic acid have been prepared in good yields for use in dental adhesives. They have been fully characterized by ¹H‐NMR, ¹³C‐NMR, ³¹P ‐ NMR, and by HRMS. All monomers are hydrolytically stable in aqueous solution. Free radical homopolymerizations of these monomers have been carried out in solution of ethanol/water (2.5/1:v/v), using 2,2′‐azo(2‐methylpropionamidine) dihydrochloride (AMPAHC) as initiator. They lead to homopolymers in moderate to excellent yields. Structure of the polymers has been confirmed by SEC/MALLS and ¹H‐NMR spectra. The photopolymerization behavior of the synthesized monomers with N,N′‐diethyl‐1,3‐bis(acrylamido)propane has been investigated by DSC. New self‐etch primers, based on these acrylamide monomers, have been formulated. Dentin shear bond strength measurements have shown that primers based on (N‐methylacrylamido)alkylphosphonic acids assure a strong bond between the tooth substance and a dental composite. Moreover, the monomer with the longest spacer group provides the highest shear bond strength. © Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7074–7090, 2008     

Synthesis,characterization, and photocuring of siloxane‐oxirane monomers

The aim of this study was to synthesize, characterize, and evaluate alternative monomers for use in dentistry. Three siloxane‐oxirane low‐shrinkage monomers were synthesized, and the products’ conversion was followed by Fourier transform ‐ infrared spectroscopy. The products obtained were characterized by ¹H and ¹³C NMR and evaluated for viscosity and a refractive index. The polymerization was evaluated by formulating two experimental photoinitiation systems, which varied for the presence of 1,2 ethanediol. A ternary system with camphorquinone (CQ), ethyl 4‐dimethylaminobenzoate (EDAB), and diphenyliodonium hexafluorphosphate (DPI) was used as control. The degree of conversion was assessed by differential scanning calorimetry (DSC). The NMR confirmed the synthesis success with 75, 87, and 55% yields for the monomers synthesized. The viscosity and the refractive index of the monomers showed favorable rheological and physical behaviors for application in dentistry. Moreover, the presence of 1,2 ‐ ethanediol increased the degree of conversion of the siloxane‐oxirane monomers. This study showed a simple and effective way to synthesize siloxane‐oxirane monomers with a high potential for application in dental materials. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1728–1733     

SYNTHESIS AND POLYMERIZATION OF 2-OXO-3-METHYLENE-5, 6-DIPHENYL-1,4-DIOXAN

A new cyclic monomer, 2-oxo-3-methylene-5, 6-diphenyl-1, 4-dioxan, was synthesized. Thestructure of the intermediates and the monomer were determined by IR,~1H NMR,~(13)C NMR andelemental analysis. This new monomer is different from other cyclic monomers in this series,it isa solid (mp 108--109℃)and not very reactive, but still can undergo free radical ring-openingpolymerization. The free radical polymerization was carried out at 130℃. The structure of theresulting polymer was discussed and charaterized by IR, ~1H NMR, ~(13)C NMR and elementalanalysis. The molecular weight of the polymer was estimated by viscosity determination.     

Synthesis,structure, and characterization of nematic liquid‐crystalline thermosets based on bisacrylates

Four bisacrylate mesogenic monomers and the corresponding liquid‐crystalline thermosets were synthesized. The chemical structures of the intermediate compounds and monomers obtained were confirmed by elemental analyses, Fourier transform infrared, and ¹H NMR and ¹³C NMR spectra. The mesomorphic properties and thermal stability were investigated with differential scanning calorimetry, thermogravimetric analysis, polarized optical microscopy, and X‐ray diffraction measurements. The influence of the curing temperatures and time on the phase behavior and thermal stability of the thermosets was discussed. All the monomers and thermosets exhibited a nematic schlieren texture. However, the monomers only showed the melting transition, and the thermosets displayed the glass transition. The experimental results demonstrated that the monomer structures strongly affected the phase behavior and the curing reaction rate, and the glass‐transition temperatures and thermal stability of the thermosets increased with the curing temperature and time. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4478–4485, 2005     

A new controllable approach to synthesize hyperbranched poly(siloxysilanes)

A new controllable approach to synthesize hyperbranched poly(siloxysilanes) via hydrosilylation of A₂‐ and B′B_x‐type monomers was developed in this work. A₂ monomers (dimethylbis(dimethylsiloxy)siloxane and tetramethyldisiloxane), B′B_x monomers (methylvinyldiallylsilane and vinyltriallylsilane), and the resultant hyperbranched poly(siloxysilanes) were well characterized using FTIR, ¹H NMR, ¹³C NMR, ²⁹Si NMR, and SEC/MALLS. The In situ FTIR results indicate that the controllable polymerization can be carried out quickly and the reaction process was obviously performed in two stages. At the first stage, silicon hydride selectively reacts with vinyl silane groups, which produces intermediate structures with one Si? H and two (or three) allyl groups. Consequently, at the second stage, these intermediates act as new AB₂ (or AB₃) type monomers and continue to be self‐polymerized to generate hyperbranched polymers. By this novel controllable approach, molecular weights and their polydispersity of the resulted hyperbranched poly(siloxysilanes) can be conveniently regulated via adjusting the process parameters, such as feeding ratio of two monomers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2708–2720, 2008     

Novel Aspects of a Convenient Synthesis and of Electroproperties of Derivatives Based on Diphenylamine

The substituted monomers 4a , c , d, 5a , b, 6a, 7a , b , and 8a of novel poly(diphenylamines), possessing the respective photochromic groups, were synthesized by the Stille cross‐coupling methodology (Scheme). The hyperbranched structures were characterized by ¹H‐ and ¹³C‐NMR spectroscopy. The obtained monomers show good stability in common organic solvents such as CHCl₃, toluene, and CH₂Cl₂, and exhibit excellent thermal stability. Electrochemical results and theoretical calculations suggest that oxidation and reduction of the monomers start from the side of the amine function and the five‐membered heterocyclic ring moieties, respectively.     

Synthesis of poly(spiropyran)s by polycondensation and their photoisomerization behaviors

Poly(spiropyran)s were synthesized by polycondensation of a bis(indoline) monomer with bis(o-positioned formyl and hydroxy)-substituted aromatic monomers in alcoholic solvents. The structures of the products and their molecular weights were determined by the ¹H NMR and GPC measurements, respectively. Furthermore, photoisomerization behaviors of the poly(spiropyran)s were analyzed by the UV–Vis and ¹H NMR measurements of their solutions in dichloromethane upon the UV and visible light irradiations.     

Synthesis and characterization of mono‐ and di‐methoxy substituted acrylate polymers containing photocrosslinkable pendant chalcone moiety

Two acrylate monomers – 4‐(2′‐methoxycinnamoyl)phenyl acrylate, and 4‐(2′,5′‐dimethoxycinnamoyl)phenyl acrylate – comprising photocrosslinkable pendant chalcone moiety and a free radical polymerizable group were synthesized. The monomers were polymerized in the presence of ethyl methyl ketone at 70°C using benzoyl peroxide as the initiator. The polymers were characterized by UV, FT‐IR, ¹H‐NMR, and ¹³C‐NMR spectra. The weight and number average molecular weights of the polymers were determined by gel permeation chromatography. The thermal stability of the polymers was studied by TGA under a nitrogen atmosphere. Glass transition temperatures of the polymers were studied by differential scanning calorimetry. The photoreactivity of the polymers was investigated for potential applications as photoresists in solution using various solvents. Copyright © 2008 John Wiley & Sons, Ltd.     

含有酯基二茂铁亚胺环钯化合物催化Suzuki和Heck反应

合成并表征了系列含有酯基二茂铁亚胺环钯化合物.结果表明,该系列环钯催化剂在纯水或有机溶剂中均能高效催化Heck和Suzuki偶联反应.     

Synthesis of hyperbranched polymers from vegetable oil based monomers via ozonolysis pathway

In this work, a variety of hyperbranched polymers (HBPs), such as hyperbranched polycarbonates, polyesters, polyurethanes and polyacetals, was successfully synthesized from castor oil and soybean oil based monomers via a A₂ + B₃ polycondensation. First, B₃ monomer triols (TriOL), trialdehydes (TriAD), and tricarboxylic acids (TriAC) were obtained by ozonolysis of castor oil and soybean oil with following reductive or oxidative treatment. Their structures were characterized by ¹H NMR and ATR‐FTIR spectroscopy as well as electrospray ionization‐Time of Flight‐mass spectrometry. These trifunctional B₃ monomers were applied in the preparation of HBPs. The resulting HBPs had number averaged molar mass (M_n) up to 9400 g/mol and weight averaged molar mass (M_w) up to 40,000 g/mol. Through adjusting the initial molar ratio of A₂ to B₃ monomers, hydroxyl terminated (from TriOL monomers) or carboxylic acid (from TriAC monomers) terminated HBPs could be obtained. All the HBPs were characterized by ¹H NMR, size exclusion chromatography, and DSC. These HBPs are potential candidates for the synthesis of cross‐linked polymeric materials or in biomedical applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2104–2114     

Generation of Photocurrent by Visible‐Light Irradiation of Conjugated Dawson Polyoxophosphovanadotungstate–Porphyrin Copolymers

Four hybrid polyoxometalate–porphyrin copolymer films were obtained by the electrooxidation of zinc octaethylporphyrin in the presence of four different Dawson‐type polyoxometalates bearing two pyridyl groups (POM(py)₂) with various spacers. The POM monomers were designed around 1,3,5‐trisubstituted benzene rings. Two of the substituents of the benzene ring are linked to the pyridyl groups, and the third is connected to the POM subunit. The four monomers vary in the relative positions of the nitrogen atoms of the pyridine rings or in the distance from the carbonyl group. The monomers were fully characterized by ¹H, ³¹P, and ¹³C NMR spectroscopy, electrospray mass spectrometry, IR and UV/Vis spectroscopy, and electrochemistry. The copolymers were characterized by UV/Vis spectroscopy, X‐ray photoelectron spectroscopy, electrochemistry, and AFM. Their photovoltaic performance under visible light irradiation was investigated by photocurrent transient measurements under visible illumination.     

Effect of spacer chemistry on the formation and properties of linear reversible polymers

A series of four pairs of bismaleimide and bisfuran monomers were combined to make thermally reversible linear polymers. The monomers were prepared using diamines having different spacer chemistries, n‐octyl, cyclohexyl, phenyl, and ethylenedioxy, such that a relatively constant spacer dimension among the four monomers was achieved. Heating of the bismaleimide/bisfuran couples resulted in low‐viscosity, easily processable liquids. Subsequent cooling to room temperature resulted in the formation of hard films, with the rate of hardening varying significantly within the series of compounds. The rate and degree of polymerization were determined using ¹H NMR spectroscopy and were both found to be dependent on the chemistry of the spacer group, as was the film rheology, which was measured using nanoindentation. Adhesion of the polymers was quantified by measurement of their tensile adhesive strength, and this was also found to be spacer dependent. Polymerization reversibility was verified using ¹H NMR spectroscopy. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5056–5066     

Poly(ether sulfone)s using a rigid dibenzothiophene dioxide heterocycle

Poly(aryl ether)s were prepared by nucleophilic aromatic substitution using conformationally restricted dichloro‐ and difluorodibenzothiophene dioxide heterocyclic monomers with bisphenol A or bisphenol AF. The heterocyclic monomers were prepared from the bis(4‐halophenyl) sulfones in two steps via lithiation followed by copper catalyzed intramolecular coupling and characterized by ¹H, ¹³C, ¹⁹F NMR spectroscopy and GC/MS. Reactivity of the fluorine containing monomer was examined using semi‐empirical methods and NMR spectroscopy measurements and found to be potentially more reactive than bis(4‐fluorophenyl) sulfone, even with a conformationally locked sulfone as the electron withdrawing group. Successful polymerizations of both the fluorine and chlorine containing monomers with bisphenol A and bisphenol AF nucleophiles were accomplished, providing polymers with number average molecular weights of approximately 45 kg/mol (difluoro monomer) and 10–20 kg/mol (dichloro monomer). The polymers exhibited high T_gs ranging from 238 to 256 °C and displayed good thermal stability with 5% degradation temperatures in air from 453–510 °C, depending on molecular weight and bisphenol composition. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3127–3131     

Interfacial synthesis of bisphenol A tetrachlorocyclotriphosphazene from bisphenol A and hexachlorocyclotriphosphazene

The effect of solvent purity on the synthesis and yield of bisphenol A tetrachlorocyclotriphosphazene (BATCCP) has not been described in the literature. The purpose of this research was to synthesize BATCCP hybrid monomers and to evaluate the effect of solvent purity on the BATCCP production. BATCCP monomers were prepared by an interfacial procedure in a water/toluene system as a function of time with the assistance of a phase transfer catalyst, tetraoctylammonium bromide. ¹H and ³¹P NMR confirmed the production of BATCCP monomer by the appearance of chemical shifts at 7.18 and 5.35 ppm in the ¹H NMR and 23.4 and 13.9 ppm in the ³¹P NMR, respectively. Distillation of the toluene, not suggested in previous reports of HCCP hybrid synthesis, resulted in an improvement of actual % yield to 40% and stability of the product throughout the 1440 min reaction as confirmed by MALDI, compared with an 11% actual yield at 15 min, decaying to 2% over a 1440 min reaction when the synthesis was performed with ‘anhydrous toluene’ as provided commercially without further distillation.     

Facile synthesis of hyperbranched polyimides from A2 + BB′2 monomers

Facile syntheses of hyperbranched polyimides were realized by the polymerization of A₂ + BB^′₂ monomers, 2,2‐bis(3,4‐dicarboxylphenyl) hexafluoropropane dianhydride (6FDA) + 2,4,6‐triaminopyrimidine (TAP), performed by mixing the monomers together in N‐methylpyrrolidone at 17% w/v concentrations with molar ratios of 6FDA:TAP ranging from 1:1 to 2:1. The lower reactivity of 2‐amino as compared with 4‐/6‐amino in TAP, demonstrated by ¹H NMR, was probably the main reason for no gelation formed during the polymerization although monomer conversions surpassed the theoretical gel points. Fourier transform infrared spectroscopy and NMR were used to verify the structures of the obtained polymers. ¹H NMR analysis indicated the degrees of branching (DB) of the polymers increased from 36 to 83% with the molar ratios of 6FDA:TAP increasing from 1:1 to 2:1. Molecular weights were determined by gel permeation chromatography, and inherent viscosities were measured. Glass‐transition temperature values, determined by differential scanning calorimetry, decreased when DB increased, and thermogravimetric analysis reflected the excellent thermal stability of the obtained hyperbranched polyimides. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4563–4569, 2002