Facile and efficient preparation of phosphinate‐functionalized aromatic diamines and their high‐Tg polyimides

Two novel phosphorus‐functionalized aromatic diamines, 1,1‐bis(4‐aminophenyl)‐1‐(6‐oxido‐6H‐dibenz <c,e> <1,2> oxaphosphorin‐6‐yl)ethane ( 1 ) and bis(4‐aminophenyl)‐(6‐oxido‐6H‐dibenz <c,e> <1,2> oxaphosphorin‐6‐yl)phenylmethane ( 2 ), were prepared from 9,10‐dihydro‐oxa‐10‐phosphaphenanthrene‐10‐oxide, 4‐aminoacetophenone, or 4‐aminobenzophenone in excess aniline using p‐toluenesulfonic acid monohydrate as catalyst by an efficient, one‐pot procedure. The effect of electron withdrawing/donating groups on the stabilization of the resulting carbocation seems critical for the success of the process and was discussed in detail. Based on diamines ( 1–2 ), a series of new polyimides, (5a–5d) and (6a–6d) , were prepared, respectively. Polyimides (5a–5d) are flexible and creasable. In contrast, polyimides (6a–6d) are brittle because of the structure rigidity, according to the analysis based on the NMR temperature‐dependent spectra of ( 2 ). Polyimides 5 displaying high T_g (318–392 °C), high moduli (3.39–4.49 GPa), low coefficient of thermal expansion (42–50 ppm/°C), and moderate thermal stability (T_d 5 wt % at 426–439 °C), are excellent high‐T_g and flame‐retardant materials. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2486–2499, 2009     

Advanced flame‐retardant epoxy resins from phosphorus‐containing diol

Phosphorus‐containing epoxy systems were prepared from isobutylbis(hydroxypropyl)phosphine oxide (IHPO) and diglycidyl ether of bisphenol A (DGEBA). Diethyl‐N,N‐bis(2‐hydroxyethyl) aminomethyl phosphonate (Fyrol 6) could not be incorporated into the epoxy backbone by a reaction with either epichlorohydrin or DGEBA because intramolecular cyclization took place. The curing behavior of the IHPO–DGEBA prepolymer with two primary amines was studied, and materials with moderate glass‐transition temperatures were obtained. V‐0 materials were obtained when the resins were tested for ignition resistance with the UL‐94 test. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3510–3515, 2005     

Synthesis of ABCD‐type miktoarm star copolymers and transformation into zwitterionic star copolymers

ABCD‐type 4‐miktoarm star copolymers of styrene (St), α‐methylstyrene (αMSt), tert‐butyl methacrylate (tBuMA), and 4‐vinylpyridine (4VP) were synthesized via anionic polymerization using 1,3‐bis(1‐phenylvinyl)benzene (m‐DDPE) as the linking molecule. The synthetic route was rationally designed with respect to the reactivity of individual propagating anion towards the double bond of m‐DDPE. Thus the synthesis includes several consecutive key reactions, for example, the monoaddition of polystyryllithium towards m‐DDPE, the polymerization of tBuMA initiated by the resulting monoadduct to produce a diblock macromonomer, the coupling of the macromonomer with poly(α‐methylstyryl)lithium to form a 3‐arm star anion, and the polymerization of 4‐vinylpyridine initiated by the star anion. These reactions were conducted either in a one‐pot process, in which the diblock macromonomer was in situ coupled with poly(α‐methylstyryl)lithium, or in a batch polymerization process, in which the same diblock macromonomer was separated. The final product was hydrolyzed to produce a zwitterionic miktoarm star copolymer, which was soluble at lower pH but insoluble in neutral and basic solution. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4818–4828, 2007     

Facile preparation of novel epoxy curing agents and their high‐performance thermosets

Two flame‐retardant epoxy curing agents, 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐yl‐tris(4‐hydroxyphenyl)methane (1) and 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐yl‐ (4‐aminophenyl)‐bis(4‐hydroxyphenyl)methane (2), were prepared by a facile, economic, one‐pot procedure. The structures of the curing agents were confirmed by IR, high‐resolution mass, 1‐D, and 2‐D NMR spectra. A reaction mechanism was proposed for the preparation, and the effect of electron withdrawing/donating effects on the stabilization of the carbocation was discussed. (1‐2) served as curing agents for diglycidyl ether of bisphenol A (DGEBA), dicyclopentadiene epoxy (HP‐7200), and cresol novolac epoxy (CNE). Properties such as glass transition temperature, coefficient of thermal expansion, thermal decomposition temperature, and flame retardancy of the resulting epoxy thermosets were evaluated. The resulting epoxy thermosets show high T_g, low thermal expansion, moderate thermostability, and excellent flame retardancy. The bulky biphenylene phosphinate pendant makes polymer chains difficult to rotate, explaining the high T_g and low thermal expansion characteristic. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7898–7912, 2008     

One‐pot synthesis of ABC miktoarm star terpolymers by coupling ATRP,ROP, and click chemistry techniques

We report on the one‐pot synthesis of well‐defined ABC miktoarm star terpolymers consisting of poly(2‐(dimethylamino)ethyl methacrylate), poly(ε‐caprolactone), and polystyrene or poly(ethylene oxide) arms, PS(‐b‐PCL)‐b‐PDMA and PEO (‐b‐PCL)‐b‐PDMA, taking advantage of the compatibility and mutual tolerability of reaction conditions (catalysts and monomers) employed for atom transfer radical polymerization (ATRP), ring‐opening polymerization (ROP), and click reactions. At first, a novel trifunctional core molecule bearing alkynyl, hydroxyl group, and bromine moieties, alkynyl(? OH)? Br, was synthesized via the esterification reaction of 5‐ethyl‐5‐hydroxymethyl‐2,2‐dimethyl‐1,3‐dioxane with 4‐oxo‐4‐(prop‐2‐ynyloxy)butanoic acid, followed by deprotection and monoesterification of alkynyl(? OH)₂ with 2‐bromoisobutyryl bromide. In the presence of trifunctional core molecule, alkynyl(? OH)? Br, and CuBr/PMDETA/Sn(Oct)₂ catalytic mixtures, target ABC miktoarm star terpolymers, PS(‐b‐PCL)‐b‐PDMA and PEO(‐b‐PCL)‐b‐PDMA, were successfully synthesized in a one‐pot manner by simultaneously conducting the ATRP of 2‐(dimethylamino)ethyl methacrylate (DMA), ROP of ε‐caprolactone (ε‐CL), and the click reaction with azido‐terminated PS (PS‐N₃) or azido‐terminated PEO (PEO‐N₃). Considering the excellent tolerability of ATRP to a variety of monomers and the fast expansion of click chemistry in the design and synthesis of polymeric and biorelated materials, it is quite anticipated that the one‐pot concept can be applied to the preparation of well‐defined polymeric materials with more complex chain architectures. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3066–3077, 2009     

Synthesis and flame retardant potential of polyols based on bisphenol‐S

Polyether polyols based on bisphenol‐S were prepared by alkoxylation and compared with analogs based on bisphenol‐A, as well as standard aromatic polyester, and polyether polyols for viscosity and temperature stability. Thermo‐oxidative stability was determined by thermo‐gravimetric analysis, pyrolysis gas chromatography/mass spectroscopy, and evolved gas analysis mass spectroscopy. Incorporation of the sulfone moiety was found to dramatically improve the thermo‐oxidative stability of the neat polyol. Significant char formation was observed with gas phase evolution of flame retardant SO₂ and aromatic sulfone only apparent at about 600 °C. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2102–2108     

Facile,one‐pot synthesis of aromatic diamine‐based phosphinated benzoxazines and their flame‐retardant thermosets

Three aromatic diamine‐based, phosphinated benzoxazines ( 7–9 ) were prepared from three typical aromatic diamines—4,4′‐diamino diphenyl methane ( 1 ), 4,4′‐diamino diphenyl sulfone ( 2 ), and 4,4′‐diamino diphenyl ether ( 3 ) by a one‐pot procedure. To clarify the reaction mechanism, a two‐pot procedure was applied, in which the reaction intermediates ( 4–6 ) were isolated for characterization. The structures of intermediates and benzoxazines were confirmed by high resolution mass, IR, and 1D and 2D‐NMR spectra. In addition to self‐polymerization, ( 7–9 ) were copolymerized with cresol novolac epoxy (CNE). After curing, the homopolymers of P( 7–9 ) are brittle while the copolymers of ( 7–9 )/CNE are tough. Dynamic mechanical analysis shows the T_gs of ( 7–9 )/CNE copolymers are 187, 190, and 171 °C, respectively. Thermal mechanical analysis shows the CTEs of ( 7–9 )/CNE copolymers are 46, 38, and 46 ppm, respectively. All the ( 7–9 )/CNE copolymers belong to an UL‐94 V‐0 grade, demonstrating good flame retardancy. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Poly (diallyldimethylammonium) and polyphosphate polyelectrolyte complexes as an all‐in‐one flame retardant for polypropylene

Poly (diallyldimethylammonium chloride) (PDDA) and ammonium polyphosphate (APP) deionized chloride ions and ammonium ions by ionizing in aqueous solution respectively, then combined to form poly (diallyldimethylammonium) and polyphosphate (PAPP) polyelectrolyte complexes as an all‐in‐one flame retardant for polypropylene and its composites were characterized by Fourier transform infrared (FTIR) spectroscopy and X‐ray photoelectron spectroscopy. One flame retardant system composed of PAPP and PP, the other flame retardant system composed of PAPP, Polyamide‐6 (PA6) and PP were tested by limiting oxygen index (LOI), UL‐94, cone calorimeter tests and thermogravimetric analysis (TGA) and compared with pure PP. The results showed that the LOI value of PP/PAPP composite can reach 27.5%, and UL‐94 V‐2 rating can be reached at 25 wt% PAPP loading. Meanwhile the cone calorimetry results displayed that the peak heat release rate (PHRR) and total heat release (THR) were reduced up to 69.3% and 22.5%, respectively, compared with those of pure PP. After adding 5 wt% PA6, the carbon source missing due to the early PAPP decomposition can be made up, and PHRR and THR can be further reduced slightly. The flame retardant mechanism of PAPP was studied by FTIR spectroscopy and X‐ray photoelectron spectroscopy. Six‐membered ring of C─N containing conjugate double bonds, cross‐linked phosphate structure formed stable, intumescent, compact char layer which greatly improved the flame retardancy of PP.     

Phase separation and permeability in polyisobutylene‐based miktoarm star polymers

The phase behavior of (PS‐PIB)₂‐s‐PAA miktoarm star terpolymers with varying volume fractions of PAA was investigated directly by transmission electron microscopy, atomic force microscopy, and small‐angle X‐ray scattering, and indirectly by thermogravimetric analysis and degree of water sorption. The microdomains of (PS‐PIB)₂‐s‐PAA demonstrate a unique and unexpected progression from highly ordered cylinders, to lower ordered spheres, to gyroid structures with increasing PAA content from 6.6 to 47 wt %. Interestingly, the phase behavior in the miktoarm star polymer system is significantly different from that reported previously for the linear counterpart of similar composition (PAA‐PS‐PIB‐PS‐PAA), where a steady progression from cylindrical to lamellar morphology was observed with increasing PAA content. At low PAA concentrations, the morphology is driven primarily by the relative solubility of the components, while at high PAA content the molecular architecture dominates. Thermal annealing demonstrated the thermodynamic stability of the morphologies, indicating the potential for design of novel microstructures for specific applications through precise control of architecture, composition, and interaction parameters of the components. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 916–925     

Facile synthesis of AB2‐type miktoarm star polymers through the combination of atom transfer radical polymerization and ring‐opening polymerization

A novel miktofunctional initiator ( 1 ), 2‐hydroxyethyl 3‐[(2‐bromopropanoyl)oxy]‐2‐{[(2‐bromopropanoyl)oxy]methyl}‐2‐methyl‐propanoate, possessing one initiating site for ring‐opening polymerization (ROP) and two initiating sites for atom transfer radical polymerization (ATRP), was synthesized in a three‐step reaction sequence. This initiator was first used in the ROP of ?‐caprolactone, and this led to a corresponding polymer with secondary bromide end groups. The obtained poly(?‐caprolactone) (PCL) was then used as a macroinitiator for the ATRP of tert‐butyl acrylate or methyl methacrylate, and this resulted in AB₂‐type PCL–[poly(tert‐butyl acrylate)]₂ or PCL–[poly(methyl methacrylate)]₂ miktoarm star polymers with controlled molecular weights and low polydispersities (weight‐average molecular weight/number‐average molecular weight < 1.23) via the ROP–ATRP sequence. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2313–2320, 2004     

Novel silicon‐containing spiroorthoester to confer combined flame retardancy and low shrinkage properties to epoxy resins

A new silicon‐containing spiroorthoester, 1,4,6‐trioxaspiro [4,4]‐2‐nonylmethyl 3‐trimethylsilyl propionate (SOE? Si), was synthesized with good yield by an esterification reaction with a previously synthesized 2‐hydroxymethyl‐1,4,6‐trioxaspiro [4,4] nonane (SOE? OH) and trimethylsilyl propionic acid. The structure of the new SOE? Si was confirmed by ¹H and ³C NMR. The SOE? Si and a mixture of DGEBA/SOE? Si were polymerized with ytterbium triflate as a cationic initiator. The curing was studied with differential scanning calorimetry (DSC) and monitored by Fourier transform infrared (FTIR) spectroscopy. The materials were characterized with DSC, termogravimetric analysis (TGA) and thermodynamomechanical analysis (DMTA). The volume change was evaluated with a Micromeritics gas pycnometer and the flame retardancy was tested by the limiting oxygen index (LOI) measurements. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4211–4224, 2007     

ABC type miktoarm star copolymers through combination of controlled polymerization techniques with thiol‐ene and azide‐alkyne click reactions

ABC type miktoarm star copolymer with polystyrene (PS), poly(ε‐caprolactone) (PCL) and poly(ethylene glycol) (PEG) arms was synthesized using controlled polymerization techniques in combination with thiol‐ene and copper catalyzed azide‐alyne “click” reactions (CuAAC) and characterized. For this purpose, 1‐(allyloxy)‐3‐azidopropan‐2‐ol was synthesized as the core component in a one‐step reaction with high yields (96%). Independently, ω‐thiol functionalized polystyrene (PS‐SH) was synthesized in a two‐step protocol with a very narrow molecular weight distribution. The bromo end function of PS obtained by atom transfer radical polymerization was first converted to xanthate function and then reacted with 1, 2‐ethandithiol to yield desired thiol functional polymer (PS‐SH). The obtained polymer was grafted onto the core by thiol‐ene click chemistry. In the following stage, ε‐caprolactone monomer was polymerized from the core by ring opening polymerization (ROP) using tin octoate as catalyst through hydroxyl groups to form the second arm. Finally, PEG‐acetylene, which was simply synthesized by the esterification of Me‐PEG and 5‐pentynoic acid, was clicked onto the core through azide groups present in the structure. The intermediates at various stages and the final miktoarm star copolymer were characterized by ¹H NMR, FTIR, and GPC measurements. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Phospha‐Michael addition to enone‐containing triglyceride derivatives as an efficient route to flame retardant renewable thermosets

A novel phosphorus‐containing vegetable oil (PETR) was prepared through phospha‐Michael addition of a diphenyl phosphine oxide to the enone derivative of high‐oleic sunflower oil (ETR). The reaction was investigated using the enone derivative of methyl oleate under conventional thermal heating and microwave irradiation. The kinetic study showed a great enhancement of reaction rate for the microwave‐initiated addition. The crosslinking of ETR with diaminodiphenylmethane (DDM) via aza‐Michael addition was also investigated under microwave irradiation, showing a noticeable acceleration of the curing. The new phosphorus‐containing triglyceride was crosslinked with DDM to obtain phosphorus‐containing vegetable oil‐based thermosets of different phosphorus contents. Limiting oxygen index values from 26.4 to 35.0 for the final materials were obtained, demonstrating that the flame retardant properties of vegetable oil‐based thermosets can be improved by adding covalently bonded phosphorus to the polymer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Diethylphosphonate‐containing benzoxazine compound as a thermally latent catalyst and a reactive property modifier for polybenzoxazine‐based resins

A diethylphosphonate‐containing benzoxazine compound (DEP‐Bz) to be used as a multi‐functional reaction agent for preparation of high performance polybenzoxazine thermosetting resins has been reported. The chemical structure of DEP‐Bz has been characterized with FTIR, ¹H NMR, and elemental analysis. The phosphonate groups of DEP‐Bz could convert into phosphonic acid groups which could catalyze the ring‐opening addition reaction of benzoxazines, to demonstrate the thermally latent catalytic effect of DEP‐Bz on the polymerization of benzoxazine compounds. Moreover, DEP‐Bz could also serve as a reactive‐type modifier for polybenzoxazines and other thermosets. DEP‐Bz modified polybenzoxazine resins have shown relatively low reaction temperature (about 190 °C), high mechanical strength with a storage modulus of about 3.0 GPa, and high flame retardancy with a limit oxygen index of about 32. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3523–3530     

The synthesis and properties of a reactive flame‐retardant unsaturated polyester resin from a phosphorus‐containing diacid

A transparent flame‐retardant unsaturated polyester resin (FR‐UPR) was obtained by reacting propylene glycol (PG) with maleic anhydride (MA), phthalic anhydride (PA), and 9,10‐dihydro‐10[2,3‐di(hydroxy carbonyl)propyl]‐10‐phosphaphenanthrene‐10‐oxide (DDP) synthesized from 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene 10‐oxide (DOPO) and itaconic acid (ITA). The chemical structure of the resulting FR‐UPR was confirmed by FTIR, ¹H‐NMR and ³¹P‐NMR. The average molecular weight and viscosity of the FR‐UPR were determined by gel permeation chromatography (GPC) and viscometer, respectively. Thermal stability was studied by thermogravimetric analysis (TGA) both in air and nitrogen to determine the thermal decomposition mechanism, and the apparent activation energy (E_a) was calculated by both the Kissinger and Ozawa methods. Compared to unsaturated polyester resin (UPR), the higher E_a of FR‐UPR3 implied an improved thermal stability. According to variations of the limited oxygen index (LOI) values, the UL 94 rating of vertical burning test and scanning electron microscopy (SEM) photographs of char residues, the flame retardance of cured FR‐UPR was enhanced with increasing DDP content. The study of fire reaction tests, using a cone calorimeter, suggested that there was a significant reduction of flammability in the FR‐UPR. Copyright © 2010 John Wiley & Sons, Ltd.     

Micelles possessing mixed cores and thermoresponsive shells fabricated from well‐defined amphiphilic ABC miktoarm star terpolymers

Amphiphilic ABC miktoarm star terpolymers consisting of polystyrene, poly(ε‐caprolactone), and poly(N‐isopropylacrylamide) arms, PS(‐b‐PNIPAM)‐b‐PCL, were synthesized via a combination of atom transfer radical polymerization, ring‐opening polymerization (ROP), and click chemistry. Difunctional PS bearing an alkynyl and a primary hydroxyl moiety at the chain end, PS‐alknyl‐OH, was prepared by reacting azido‐terminated PS with an excess of 3,5‐bis(propargyloxy)benzyl alcohol (BPBA) under click conditions. The subsequent ROP of ε‐caprolactone using PS‐alknyl‐OH macroinitiator afforded PS(‐alkynyl)‐b‐PCL copolymer bearing an alkynyl moiety at the diblock junction point. Target PS(‐b‐PNIPAM)‐b‐PCL amphiphilic ABC miktoarm star terpolymers were then prepared via click reaction between PS(‐alkynyl)‐b‐PCL and an excess of azido‐terminated PNIPAM (PNIPAM‐N₃). The removal of excess PNIPAM‐N₃ was accomplished by “clicking” onto alkynyl‐functionalized Wang resin. All the intermediate and final products were characterized by gel permeation chromatography, ¹H NMR, and FTIR. In aqueous solution, the obtained amphiphilic ABC miktoarm star terpolymer self‐assembles into micelles possessing mixed PS/PCL cores and thermoresponsive shells, which were further characterized by dynamic laser light scattering and transmission electron microscopy. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1636–1650, 2009     

Synthesis of high‐order multiblock core cross‐linked star polymers

Core cross‐linked star (CCS) polymers with radiating arms composed of high‐order multiblock copolymers have been synthesized in a one‐pot system via iterative copper‐mediated radical polymerization. The employed “arm‐first” technique ensures the multiblock sequence of the macroinitiator is carried through to the star structure with no arm defects. The versatility of this approach is demonstrated by the synthesis of three distinct star polymers with differing arm compositions, two with an alternating ABABAB block sequence and one with six different block units (i.e. ABCDEF). Owing to the star architecture, CCS polymers in which the arm composition consists of alternating hydrophilic–hydrophobic (ABABAB) segments undergo supramolecular self‐assembly in selective solvents, whereas linear polymers with the same block sequence did not yield self‐assembled structures, as evidenced by DLS analysis. The combination of microstructural and topological control in CCS polymers offers exciting possibilities for the development of tailor‐made nanoparticles with spatially defined regions of functionality. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 135–143     

Facile synthesis for well‐defined A2B miktoarm star copolymer of poly(3‐hexylthiophene) and poly(methyl methacrylate) by the combination of anionic polymerization and click reaction

We have introduced a facile synthetic route for well‐defined A₂B miktoarm star copolymer composed of regioregular poly(3‐hexylthiophene) and poly(methyl methacrylate) ((P3HT)₂PMMA) by the combination of anionic polymerization and click reaction. First, we synthesized PMMA terminated with 1,3,5‐tris(bromomethyl)benzene (PMMA‐(Br)₂) by anionic polymerization, and two bromines attached to the end of the PMMA chains were replaced by azides (PMMA‐(N₃)₂). Also, monoethynyl‐capped P3HT was synthesized by Grignard metathesis polymerization and post‐end functionalization. Then, copper(I)‐catalyzed Huisgen 1,3‐dipolar cycloaddition click reaction between monoethynyl‐capped P3HT and PMMA‐(N₃)₂ was performed to synthesize (P3HT)₂PMMA. We used a slightly excess amount of monoethynyl‐capped P3HT so that all of the azide groups at the end of the PMMA chains completely reacted with monoethynyl‐capped P3HT. After complete removal of unreacted monoethynyl‐capped P3HT by column chromatography, pure (P3HT)₂PMMA with narrow molecular weight distribution (the polydispersity of 1.18) was obtained. The weight fraction of P3HT and the total molecular weight of (P3HT)₂PMMA are 0.48 and 16,000, respectively. To investigate the effect of the chain architecture on optical property and thin‐film morphology, we synthesized two linear P3HT‐b‐PMMAs (P3HT‐b‐PMMA‐L and P3HT‐b‐PMMA‐H) with similar weight fraction of P3HT block (0.48 for P3HT‐b‐PMMA‐L and 0.45 for P3HT‐b‐PMMA‐H) but two different total molecular weights (7900 for P3HT‐b‐PMMA‐L and 15,300 for P3HT‐b‐PMMA‐H). UV–visible (UV–vis) absorption spectrum and the fibril width of (P3HT)2PMMA thin film were similar to those of P3HT‐b‐PMMA‐L thin film. However, UV–vis spectrum for P3HT‐b‐PMMA‐H thin film was red‐shifted and the fibril width of P3HT‐b‐PMMA‐H was much larger than that of (P3HT)₂PMMA. This indicates that the π–π interaction between P3HT arms in (P3HT)₂PMMA is strong enough to arrange two P3HT backbone chains in (P3HT)₂PMMA to stack one by one along the nanofibril axis. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

A bio‐safe cyclophosphazene derivative flame retardant for polylactic acid composites: Flammability and cytotoxicity

An efficient bio‐safe cyclophosphazene flame retardant, 1,5,9,13,16,20‐Hexaoxa‐7,14,21‐triaza‐6λ⁴,8λ⁴,5λ⁴‐triphosphatrispiro[5.1.5.1.5.1]heneicosa‐6,8(14),15(21)‐triene (HCPO), was synthesized, and then was incorporated into polylactic acid (PLA) to improve the fire safety. The chemical structure of HCPO was confirmed by Fourier‐transformed infrared spectroscopy, mass spectrometry, and nuclear magnetic resonance spectroscopy. The thermal stability of the compound was characterized by thermogravimetric (TG) analyzer. The cytotoxic effects of HCPO to cells were evaluated. Fire behavior and thermal stability of PLA composites were investigated by vertical burning, limiting oxygen index (LOI), TG analysis, and cone calorimeter. The morphology of residual charring was observed by scanning electron microscope. The results showed HCPO was bio‐safe, and highly effective to enhance the flame retardancy of PLA composites. The LOI value was increased from 18.4 to 27.5 and UL‐94 grade achieved V‐0 for the PLA composite containing only 2% HCPO and 2% pentaerythrotol. It was demonstrated that intermolecular cross‐linking reaction between pentaerythrotol and HCPO in high temperature range could accelerate the formation of compact char layers.     

Syntheses and characterization of 16‐arm star and star diblock copolymer and AB8 9‐miktoarm star copolymer via NMRP and ROP from dendritic multifunctional macroinitiators

A dendritic macroinitiator having 16 TEMPO‐based alkoxyamines, Star‐16 , was prepared by the reaction of a dendritic macroinitiator having eight TEMPO‐based alkoxyamines, [G‐3]‐OH , with 4,4′‐bis(chlorocarbonyl)biphenyl. The nitroxide‐mediated radical polymerization (NMRP) of styrene (St) from Star‐16 gave 16‐arm star polymers with PDI of 1.19–1.47, and NMPR of 4‐vinylpyridine from the 16‐arm star polymer gave 16‐arm star diblock copolymers with PDI of 1.30–1.43. The ring‐opening polymerization of ε‐caprolactone from [G‐3]‐OH and the subsequent NMRP of St gave AB₈ 9‐miktoarm star copolymers with PDI of 1.30–1.38. The benzyl ether linkages of the 16‐arm star polymers and the AB₈ 9‐miktoarm star copolymers were cleaved by treating with Me₃SiI, and the resultant poly(St) arms were investigated by size exclusion chromatography (SEC). The SEC results showed PDIs of 1.23–1.28 and 1.18–1.22 for the star polymers and miktoarm stars copolymers, respectively, showing that they have well‐controlled poly(St) arms. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1159–1169, 2007.