Vinyl monomers bearing chromophore moieties and their polymers. IX. Initiation and photochemical behavior of water and liposoluble acrylic monomers having pyrimidinyl moiety and their polymers

Two acrylic monomers bearing a pyrimidinyl moiety, N‐acryloyl‐N′‐2‐pyrimidinylpiperazine (APMP) and N‐methacryloyl‐N′‐2‐pyrimidinylpiperazine (MPMP), are prepared by reactions of N‐2‐pyrimidinylpiperazine with corresponding acryloyl chlorides in the presence of triethylamine. APMP and MPMP can be polymerized either by using radical initiators such as azobisisobutylonitrile or potassium persulfate (KPS) or by UV light irradiation without any sensitizer. APMP, MPMP, and their polymers are water soluble and liposoluble. They can act as sensitizers to initiate the photopolymerizations of acrylonitrile (AN) in DMF and acrylamide (AAm) or N‐acryloylmorpholine (AMPL) in an aqueous medium. They can also act as one component of a redox initiation system by combining with KPS to initiate the polymerization of AAm in an aqueous medium, and a superhigh molecular weight up to 10⁶–10⁷ for P(AAm) or 10⁵–10⁶ for P(AMPL) is obtained. The above polymerizations are pursued kinetically. The mechanism of the photopolymerizations initiated by MPMP or P(MPMP) are confirmed by an electron spin resonance study. By the fluorescent analysis of PAN and P(AAm) initiated by MPMP, APMP, or their polymers we confirm that they not only initiate the polymerization but also enter the polymer chains. The fluorescence spectra of MPMP, APMP, and their polymers are recorded. A fluorescence structural self‐quenching effect is also observed. The fluorescence of P(MPMP) can be quenched by adding electron‐deficient unsaturated compounds such as methacrylonitrile, AN, fumaronitrile, tetracyanoethylene, methyl acrylate, and methyl methacrylate and the correlation between the Stern–Volmer constants and the electron deficiency of the quenchers is described. The fluorescence quenching of P(MPMP) by a water‐soluble C₆₀ derivative is also demonstrated. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 19–28, 2000     

Vinyl monomers bearing chromophore moieties and their polymers. VI. Synthesis and photochemical behavior of acrylic monomer bearing phenoxazine moiety and its polymer

An acrylic monomer having phenoxazine moiety, i.e., N-acryloylphenoxazine (APO), has been synthesized by dehydrochlorination of N-(3-chloropropionyl)phenoxazine with 1,5-diazabicyclo[5.4.0]undec-5-ene in dimethyl sulfoxide. The monomer can be polymerized with AIBN as an initiator. The photochemical behavior, including the fluorescence and photosensitizing properties of this monomer and its polymer, has been studied. It has been recorded that the absorption spectrum of polymer P(APO) displays a few blue shifts compared with its monomer APO. It has also been observed that the fluorescence emission intensity of the monomer is dramatically lower than that of its polymer at the same chromophore concentration. This may be ascribed to the charge transfer interacting between the coexisting electron-accepting acrylic carbon-carbon double bond and the electron-donation phenoxazine moiety in APO, intramolecularly or intermolecularly on excitation. The fluorescence of the APO polymer, which does not have carbon-carbon double bond, can be quenched by electron-deficient unsaturated nitriles and esters, clarifying that the electron-deficient carbon-carbon double bond does play an important role for the fluorescence quenching of the monomer. Thus, we term such phenomena as structural self-quenching effect, differing from the concentrational self-quenching effect, which is caused mainly by concentrational factors. The fluorescence quenching of P(APO) by C₆₀ has also been demonstrated. The formation of the charge transfer complex of P(APO) with C₆₀ in the ground state is revealed by the upward deviation from the linearity of the Stern-Volmer plot. APO can act as a photoinitiator to sensitize the photopolymerization of vinyl monomers such as acrylonitrile in dimethyl formamide and pursued kinetically. From the ultraviolet analysis of the PAN sensitized by APO, it is proved that APO not only sensitizes the photopolymerization of AN, but also incorporates in the PAN chain. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:481–489, 1997     

Novel fluorinated polymers bearing phosphonated side chains: synthesis, characterization and properties

A new class of aryl trifluorovinyl ether monomers containing phosphonated oligo(ethylene oxide) units were designed and synthesized. Novel fluorinated polymers containing perfluorocyclobutane and phosphonic acid moieties were prepared from these monomers via the thermal cyclopolymerization and hydrolysis reaction. The structures of these monomers and polymers were characterized by nuclear magnetic resonance spectroscopy and fourier transform spectroscopy. The thermal properties of these polymers were evaluated with differential scanning calorimetry and thermo-gravimetric analysis. The 5% weight loss of these polymers was in range of 258–270 °C in nitrogen, but no glass transition temperatures were detected. The polymers showed good solubility in organic solvents such as dimethyl sulfoxide and N,N-dimethylacetamide. In addition, the basic membrane properties of the membranes such as water uptake and proton conductivity were also measured at room temperature. The membranes exhibited high water uptake (up to 44.7%) due to the high level of phosphonation content. The proton conductivities of the membranes under 100% relative humidity were in the range of 0.032–0.068 S/cm, which entitled them as candidates for proton exchange membranes.     

Novel regenerable N‐halamine polymeric biocides. I. Synthesis,characterization, and antibacterial activity of hydantoin‐containing polymers

Two novel cyclic‐amine monomers, i.e., 3‐allyl‐5,5‐dimethylhydantoin (ADMH) and 7,8‐benzo‐3 allyl‐1,3‐diazasprio[4.5]decane‐2,4‐dione (BADDD) were synthesized with good yields by reacting allyl bromide with 5,5‐dimethylhydantoin (DMH) and 7,8‐benzo‐1,3‐diazasprio[4.5]decane‐2,4‐dione (BDDD), respectively. The synthesized monomers were characterized by FTIR and ¹H‐NMR spectra, and copolymerized with acrylonitrile (AN), vinyl acetate (VAC), and methyl methacrylate (MMA) in a small monomer ratio of ADMH and BDDD, respectively. The copolymers were characterized by FTIR, ¹H‐NMR, and DSC studies. The N‐halamine derivatives of the corresponding copolymers were found to exhibit high antibacterial activities against Escherichia coli, and the antibacterial properties were durable and regenerable. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2460–2467, 2001     

Design,Synthesis, and in vitro Evaluation of Tubulin-Targeting Dibenzothiazines with Antiproliferative Activity as a Novel Heterocycle Building Block

We prepared a series of free NH and N-substituted dibenzonthiazines with potential anti-tumor activity from N-aryl-benzenesulfonamides. A biological test of synthesized compounds (59 samples) was performed in vitro measuring their antiproliferative activity against a panel of six human solid tumor cell lines and its tubulin inhibitory activity. We identified 6-(phenylsulfonyl)-6H-dibenzo[c,e][1,2]thiazine 5,5-dioxide and 6-tosyl-6H-dibenzo[c,e][1,2]thiazine 5,5-dioxide as the best compounds with promising values of activity (overall range of 2–5.4 μM). Herein, we report the dibenzothiazine core as a novel building block with antiproliferative activity, targeting tubulin dynamics.     

Synthesis, characterization and photoconductive properties of optically active methacrylic polymers bearing side-chain 9-phenylcarbazole moieties

The synthesis of two novel optically active monomers containing 9-phenylcarbazole moieties, such as (S)-(+)-2-methacryloyloxy-N-[4-(9-carbazolyl)phenyl]succinimide [(S)-(+)-MCPS] and (S)-(+)-3-methacryloyloxy-N-[4-(9-carbazolyl)phenyl]pyrrolidine [(S)-(+)-MCPP], is described. Each monomer has been radically homopolymerized to afford the corresponding optically active polymeric derivatives, which have been fully characterized. Their spectroscopic, thermal and photoconductive properties were compared to those of the new achiral homopolymer poly[N-(2-methacryloyloxyethyl)-N-[4-(9-carbazolyl)phenyl]ethylamine] {poly[MCPE]}, devised as an optically inactive macromolecular model compound, as well as to analogue polymeric derivatives containing side-chain optically active carbazolyl moieties. The chiroptical properties of the chiral polymers are quantitatively higher than in the corresponding monomers. Owing to the substantially stereoirregular structure of the main chain, this suggests that the overall optical activity is mainly due to conformational dissymmetry of the macromolecules. Spectroscopic evidence suggests the presence in all polymeric derivatives of dipole-dipole interactions between the 9-phenylcarbazolyl chromophores, occurring as a consequence of their anchorage to the polymer backbone, which favours their aggregation and justifies their high decomposition temperatures.     

Enantioface differentiation by chiral polymers containing dimethylaminobornyl moieties

Chiral monomers cis,endo-3-dimethylamino-2-bornyl methacrylate (DABM) and N,N-dimethyl[cis,endo-2-(2-vinyloxy-ethoxy)-3-bornyl]amine (DVEBA) were synthesized from (+)-camphor. The homopolymerization of both DABM and DVEBA, and the copolymerization of both chiral monomers with achiral methylmethacrylate (MMA) and styrene (St) were carried out with 2,2-azobisisobutyronitrile (AIBN) in various organic solvents. Effects of temperature, solvents, reagent molar ratio and reaction time on the polymerizations were studied. Dependences of the feeding concentration and reaction conditions on the specific rotation of the chiral copolymers were investigated. Enantioface differentiation by using the chiral polymers having dimethylaminobornyl moieties synthesized in this investigation were investigated. Effects of temperature and solvent on the asymmetric induction were also studied. © 1994 John Wiley & Sons, Inc.     

Monomers for adhesive polymers: 11. Structure–adhesive properties relationships of new hydrolytically stable acidic monomers

The synthesis of six new hydrolytically stable acidic monomers is described. Those monomers are N,N‐disubstituted acrylamides bearing either a phosphonic acid group or a diphosphonic acid group. They were fully characterized using ¹H NMR, ¹³C NMR and ³¹P NMR spectroscopy and high‐resolution mass spectrometry. The copolymerization of each acidic monomer with N,N′‐diethyl‐1,3‐bis(acrylamido)propane was investigated using photo‐differential scanning calorimetry. Self‐etching enamel–dentin adhesives were formulated and evaluated in terms of both dentin and enamel adhesion. The influence of the monomer structure (nature of either the spacer or the acidic group, nature of the acrylamide substitution) on the adhesive properties is discussed. The adhesives based on 10‐(N‐ethylacrylamido)decylphosphonic acid and 10‐(N‐methylacrylamido)decylbisphosphonic acid are able to achieve a strong bond between a dental composite and both dentin and enamel. © 2013 Society of Chemical Industry     

Synthesis and characterization of novel organotin monomers and copolymers and their antibacterial activity

Two novel organotin monomers, (N‐tri‐n‐butyltin) maleimide and m‐acryloylamino‐(tri‐n‐butyltin benzoate), were synthesized. Copolymerization of these two monomers with styrene was carried out in the bulk at 65°C using asobisisobutyronitrile as the free radical initiator. The monomers and copolymers were characterized by elemental analysis; the molecular weights of the copolymers were determined by GPC, solubility, IR, and ¹H‐NMR spectral studies. The antibacterial activities of the synthesized organotin monomers and copolymers toward various types of bacteria were also reported. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 740–745, 2000     

New poly(amide imide)s containing bis(4‐trimellitimidophenyl) sulfone and hydantoin moieties in the main chain: Synthesis and properties

Several new poly(amide imide)s were synthesized through the polycondensation reactions of bis(4‐trimellitimidophenyl) sulfone [N,N′‐(4,4′‐diphenylsulfone) bistrimellitimide] with a number of hydantoin derivatives in a medium consisting of thionyl chloride, N‐methyl‐2‐pyrrolidone, and pyridine. The polycondensations produced a series of novel poly(amide imide)s in high yields with inherent viscosities of 0.20–0.46 dL/g. The resulting poly(amide imide)s were characterized with elemental analysis, viscosity measurements, thermogravimetric analysis, derivative thermogravimetry, solubility testing, and Fourier transform infrared spectroscopy. All the polymers were soluble at room temperature in polar solvents such as N,N‐dimethylacetamide, N,N‐dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, and N‐methyl‐2‐pyrrolidone. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1776–1782, 2005     

Synthesis, characterization and third-order non-linear optical properties of novel fluorene monomers and their cross-conjugated polymers

We designed and synthesized two novel fluorene monomers of D-A-D (donor-acceptor-donor) type (M1 and M2), and their two corresponding polymers (PM1 and PM2) and a copolymer (CPM). These high molecular weight, film-forming polymers were obtained from metal-free, superacid-catalyzed reactions of the monomers with N-phenylisatin. The cubic NLO response (χ⁽³⁾) for these new compounds, in solid thin films, was measured through the use of third-harmonic generation (THG) Maker-Fringes technique at IR wavelengths given values of the order of 10⁻¹² esu from which, the corresponding second hyperpolarizabilities (γ) were estimated to be of the order of 10⁻³³ esu for monomers and 10⁻³¹ esu for polymers. Second hyperpolarizabilities have also been estimated theoretically at B3LYP/6-31G(d) level of theory in gas phase and related with the electronic structure of the synthesized molecules.     

Synthesis and properties of novel vinyl polymers bearing azacrown ether side chain

Summary Novel vinyl polymers bearing monoazacrown ether-type side chains with a number average molecular weigh of over 5000 were radically synthesized from the 16-membered α-methylenemacrolide monomers. The obtained polymers possessed a Na⁺ or K⁺ selective extraction ability, whereas K⁺ was preferentially extracted by the monomers. The polymer having the N-(2-naphthoyl)azacrown ether pendant groups showed a selective UV-responsive complexation with Li⁺ in 1,2-dichloroethane-CH₃CN.     

Preparation and properties of polymers of secondary alkyl crotonates and related monomers

The anionic polymerization of a variety of secondary alkyl crotonates and related monomers initiated by fluorenyllithium (complexed with tetrahydrofuran) in toluene at ?78°C. is reported. No crystallinity could be developed in any of the samples, and nuclear magnetic resonance was uniformative about possible tacticity. The polymerization techniques were ineffective when applied to n-alkyl esters. Polymer was obtained from isopropyl cinnamate and N,N-dimethyl crotonamide, but not from isopropyl thiocrotonate or isopropyl 2-pentenoate. The physical properties of injectionmolded specimens of polymers of isopropyl, s-butyl and cyclohexyl crotonate were examined in some detail; the polymers exhibited a desirable combination of high service temperatures and good impact resistance for a vinyl homopolymer but were extremely difficult to mold. Poly(isopropyl crotonate) had a heat distortion temperature of 125°C. at 85 psi, a notched Izod impact of 2.4 ft.-lb./in. of notch, and a flexural modulus of 274,000 psi.     

One-dimensional coordination polymers based on first-row transition metals: A solid-state study of weak backbone interactions

We present further data on the solid-state structures of one-dimensional coordination polymers based upon dipositive transition metal hexafluoro-acetylacetonate (hfacac) complexes. A variety of linking subunits are employed in order to investigate and probe the relatively weak interactions that make up the backbones of these polymers. Reported in this study are metal complexes containing manganese, zinc, copper, and cobalt and a range of donor building blocks encompassing an array of bonding motifs, including pyridyl—metal, pyridyl(N-oxide)—metal, and hydrogen bonding. The specific linkers utilized are 4,4′-dipyridyl N,N′-dioxide hydrate, 2,5-bis(4-ethynylpyridyl)furan, 4,4′-trimethylenedipyridine, and trans-1-(2-pyridyl)-2-(4-pyridyl)-ethylene. A detailed discussion of the products is presented, as is a comparison to known compounds of a similar nature. All compounds are characterized via single-crystal X-ray diffraction and elemental analysis for the bulk of the sample.     

Synthesis and characterization of soluble copoly(arylene ether sulfone phenyl-s-triazine)s containing phthalazinone moieties in the main chain

A series of new poly(arylene ether sulfone phenyl-s-triazine) copolymers containing phthalazinone moieties in the main chain (PPESPs) were prepared by a direct solution polycondensation of 4-(4-hydroxylphenyl)(2H)-phthalazin-1-one (HPPZ) with 2-phenyl-4,6-bi(4-fluorophenyl)-1,3,5-triazine (BFPT) and 4,4′-dichlorodiphenyl sulfone (DCS). Model reactions monitored by HPLC indicated that BFPT had slightly higher reactivity than DCS in nucleophilic displacement reactions. The obtained random copolymers were characterized by FTIR, NMR, elemental analysis and GPC. The presence of sulfone and phthalazinone in the polymer chain results in an improvement in the solubility of poly(arylene ether phenyl-s-triazine)s in common organic solvents, such as N-methylpyrrolidone, N,N-dimethyl acetamide (DMAc), chloroform, sulfolane and pyridine. Thermal analysis reveal that the copolymers exhibit high glass transition temperatures (T_gs) ranging from 271–300 °C, and excellent thermal stability associated with decomposition temperatures for 5% mass-loss exceeding 503 °C. All copolymers are amorphous except PPESP28 as evidenced by WAXD. Their T_gs and solubility increase with an increase in sulfone content in the polymer backbone, while the crystallinity and overall thermal stability appear to decrease. This kind of phthalazinone-based copoly(arylene ether sulfone phenyl-s-triazine)s may be considered a good candidate for using as high-performance structural materials.     

Antimicrobial effect of monomers and polymers with azole moieties

Five monomers with azole moieties were synthesized and their antimicrobial activities were investigated. The antimicrobial activity of the monomers was evaluated by the halo zone test method. The results strongly depended on the chemical structure of the group attached to the azole moieties. Polymers with (benzimidazol‐2‐yl)thio groups and with (5‐methyl‐1,3,4‐thiadiazol‐2‐yl)thio groups were synthesized. The shake flask test showed that the two polymers possessed excellent antimicrobial activity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2933–2937, 2003     

Novel amphiphilic diblock copolymers bearing acid-labile oxazolidine moieties: Synthesis, self-assembly and responsive behavior in aqueous solution

A novel oxazolidine based acid-labile monomer N-acryloyl-2,2-dimethyl-1,3-oxazolidine (ADMO) was synthesized and polymerized by reversible addition fragmentation chain transfer (RAFT) polymerization using poly(ethylene glycol) based chain transfer agent (PEG-CTA). The diblock copolymers PEG-b-PADMO were composed of hydrophilic PEG with fixed length and hydrophobic PADMO with different lengths, which formed core-shell micelles in water. Morphologies and sizes of micelles were obtained by transmission electron microscopy (TEM) and dynamic light scattering (DLS), which showed that the shapes of polymeric aggregates developed from small spherical micelles, worm-like micelles to larger size of vesicles, as the length of PADMO increased. The hydrolysis kinetics of the micelles was studied using ¹H NMR, DLS and release of loaded Nile Red dye, whose rate strongly depended on pH and micellar structure. It led to the disruption of polymeric micelles and concomitant release of the guest molecules, due to the transformation of hydrophobic PADMO into hydrophilic poly(2-hydroxyethyl acrylamide) (PHEAM).     

Synthesis and properties of new poly(amide imide)s containing trimellitic rings and hydantoin moieties in the main chain under microwave irradiation

Trimellitic anhydride was reacted with 4,4′‐diaminodiphenyl ether in a mixture of acetic acid and pyridine (3 : 2) at room temperature and was refluxed at 90–100°C, and N,N′‐(4,4′‐diphenylether) bistrimellitimide (3) was obtained in a quantitative yield. 3 was converted into N,N′‐(4,4′‐diphenylether) bistrimellitimide diacid chloride (4) by a reaction with thionyl chloride. Then, six new poly(amide imide)s were synthesized under microwave irradiation with a domestic microwave oven through the polycondensation reactions of 4 with six different derivatives of 5,5‐disubstituted hydantoin in the presence of a small amount of a polar organic medium such as o‐cresol. The polycondensation proceeded rapidly and was completed within 7–10 min, producing a series of new poly(amide imide)s in high yields with inherent viscosities of 0.27–0.66 dL/g. The resulting poly(amide imide)s were characterized by elemental analysis, viscosity measurements, differential scanning calorimetry, thermogravimetric analysis, derivative thermogravimetry, solubility testing, and Fourier transform infrared spectroscopy. All the polymers were soluble at room temperature in polar solvents such as N,N‐dimethylacetamide, N,N‐dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, and N‐methyl‐2‐pyrrolidone. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3447–3453, 2004     

Synthesis and characterization of n-type conjugated copolymers bearing perylene diimide moieties

Three electron-deficient conjugated polymers based on perylene diimide (PDI) units, namely, poly[(N,N′-didodecyl-3,4,9,10-perylene diimide-1,7-diyl)-alt-(9,9-dihexylfluorene-2,7-diyl)] (PPDIF), poly{(N,N′-didodecyl-3,4,9,10-perylene diimide-1,7-diyl)-alt-[N-(2-ethylhexyl) carbazole-3, 6-diyl]} (PPDIC) and poly{(N,N′-didodecyl-3,4,9,10-perylene diimide-1,7-diyl)-co-[N-(2-ethylhexyl) carbazole-3,6-diyl]-co-(9,9-dihexylfluorene-2,7-diyl)} (PPDICF) have been synthesized via Suzuki coupling reaction, and their chemical structures are confirmed by ¹H NMR, ¹³C NMR and FT-IR. All these polymers show broad absorption bands in 250–700 nm, and their optical band gaps are calculated to be ~1.7 eV. Cyclic voltammetry results confirm that the objective macromolecules possess high electron affinity of ~3.9 eV. By employing poly-3-hexylthiophene (P3HT) as electron donor and PPDIC as electron acceptor, all polymer solar cells (aPSCs) with bulky heterojunction structure have been fabricated, preliminary results indicate they have one of the most highest open-circuit voltage (V _oc) (0.86 V) reported so far in aPSCs with PDI-based polymers as electron acceptor.     

Photografting of PVC containing N,N‐diethyldithiocarbamate groups with vinyl monomers

Poly(vinyl chloride) (PVC) with pendent N,N‐diethyldithiocarbamate groups (PVC–SR) was prepared through the reaction of PVC with sodium N,N‐diethyldithiocarbamate (NaSR) in butanone and used as a photoinitiator for the grafting polymerization of three vinyl monomers [styrene (St), methyl methacrylate (MMA), and acrylamide (Am)]. The effects of ultraviolet (UV) irradiation time, PVC–SR amount, and the monomer amount on grafting and grafting efficiency were investigated. The results showed that PVC–SR could initiate the polymerization of three vinyl monomers effectively and obtained crosslinked copolymers. The grafting and grafting efficiency of styrene and methyl methacrylate were higher than those of acrylamide. The polymerization activity of three monomers was acrylamide > methyl methacrylate > styrene. By analyzing the UV spectrum of PVC–SR with a different irradiation time, it was confirmed that PVC–SR was dissociated mainly into macromolecular the sulfur radical PVC–S · and the small molecular carbon radical · C(S)N(C₂H₅)₂; the grafting polymerization mechanism was discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2569–2574, 2000