Improvement of surface wettability and interfacial adhesion ability of poly(p-phenylene benzobisoxazole) (PBO) fiber by incorporation of 2,5-dihydroxyterephthalic acid (DHTA)

By introducing 2,5-dihydroxyterephthalic acid (DHTA) into poly(p-phenylene benzoxazole) (PBO) macromolecular chains, dihydroxy poly(p-phenylene benzobisoxazole) (DHPBO) was synthesized and then DHPBO fibers were prepared by dry-jet wet-spinning method. Effects of hydroxyl polar groups on surface wettability and interfacial adhesion ability of PBO fiber were investigated. With the incorporation of double hydroxyl polar groups, contact angle on PBO fiber for water can decrease from 71.4° to 50.70°, and contact angle for ethanol can decrease from 37.2° to 27.40°. The wetting time on DHPBO fibers for water can be as short as 650 ms, which is half of that of PBO fibers. The interfacial shearing strength (IFSS) between DHPBO (10% mol content DHTA) fibers and epoxy resin is 18.87 MPa, 92.55% higher than that of PBO fibers. SEM images indicate that the PBO/epoxy composite failure mode may change from fiber/matrix adhesive failure to partially cohesive failure.     

Novel conjugated polymer poly(benzobisoxazole-2,6-diylvinylene): synthesis and evidence of aggregate formation in methanesulfonic acid

A new conjugated polymer poly(benzobisoxazole-2,6-diylvinylene) (PBOV) has been synthesized as an analogue of poly(p-phenylene benzobisoxazole) (PBO). The comparison between PBOV and PBO has been carried out by Fourier transform infrared spectroscopy, thermogravimetric analysis, UV, and photoluminescence (PL) spectroscopy. The UV absorption peaks, PL excitation and emission wavelengths of PBOV have a significant red-shift due to the better electronic delocalization. Similar to PBO, it can be observed in the PL spectra of PBOV at various concentrations in methanesulfonic acid (MSA) that the intensity of emission was depressed and the highly structured emission spectra gradually changed to featureless, red-shifted, and broad spectra with increasing concentration. The change in emission spectra can be attributed to the existence of the interchain aggregates, although PBOV does not show highly ordered structure as PBO does.     

聚芴基苯并唑类共聚物的合成和光物理性能

通过溶液缩聚法合成了一系列不同组分的无规共聚物--聚对苯撑苯并二噁唑-co-聚(9,9-二辛基芴苯并二噁唑)(PBO-co-PBOF).利用X射线衍射、紫外-可见光吸收光谱、光致荧光光谱研究了不同组分和结构变化对聚合物形态和光物理性能的影响.结果表明:聚合物主链上辛基芴基团的引入使聚合物结构从晶态转变为非晶态.共聚物分...     

UV accelerated aging and aging resistance of dihydroxy poly(p‐phenylene benzobisoxazole) fibers

By introducing binary hydroxyl groups into poly(p‐phenylene benzoxazole) (PBO) macromolecular chains, we synthesized dihydroxy poly(p‐phenylene benzobisoxazole) (DHPBO) polymers and then prepared DHPBO fibers by dry‐jet wet‐spinning. Comparative studies were performed between intrinsic PBO fibers and DHPBO fibers. The effects of hydroxyl polar groups on improving the UV aging resistance of PBO fibers were investigated. With the introduction of hydroxyl groups, substantial changes in the chemical structures and surface morphologies of DHPBO fibers were observed. As proved by tensile testing and intrinsic viscosity measurement, the UV resistance of DHPBO fibers is obviously improved compared to that of intrinsic PBO fibers. XRD results indicate that the UV aging of these fibers occurs mainly on the surfaces of fibers. Based on these results, the mechanism of UV aging of PBO fibers was discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

主链含羟基的芳杂环液晶共聚物聚对苯撑苯并二噁唑的 合成及性能研究

通过在聚合过程中添加少量2,5-二羟基对苯二甲酸(DHTA)部分替代对苯二甲酸(TPA)与4,6-二氨基间苯二酚(DAR)盐酸盐进行共聚, 合成了一系列大分子链上含有羟基基团的DHPBO共聚物, 并制得其初生纤维. 利用FTIR、接触角等分析手段对其化学结构和纤维表面性能进行了表征, 通过单丝拔出实验和SEM考察了DHPBO纤维与环氧树脂基体的界面剪切强度, 并采用轴向压缩弯曲实验和紫外光加速老化实验评价了羟基基团的引入对提高纤维压缩性能和抗紫外性能的影响. 结果表明, 羟基基团的引入使得DHPBO纤维的表面亲水性、与环氧树脂的界面剪切强度以及纤维的压缩性能和抗紫外性能都有了显著提高.     

In situ polymerization and characterization of graphene oxide‐co‐poly(phenylene benzobisoxazole) copolymer fibers derived from composite inner salts

A facile and efficient strategy for preparing well dispersed graphene oxide (GO)‐co‐Poly(phenylene benzobisoxazole) (PBO) copolymer fibers was carried out by direct in situ polycondensation of composite inner salts. The composite inner salts were achieved to improve the dispersivity, solubility, reactivity, and interfacial adhesion of GO in PBO polymer matrix. The structure and morphology of GO‐co‐PBO copolymer fibers have been characterized. It was demonstrated that GO were covalently incorporated with PBO molecular chains and dispersed considerably well in PBO fiber even the GO reach to 3 wt %. Meanwhile, the tensile modulus, tensile strength and thermal stability of GO‐co‐PBO copolymer fibers increased considerably with GO. The mechanism and theoretical calculation of GO enhanced PBO fiber were also discussed. The main reasons for the improvement on performance of PBO fiber should be attributed to good dispersion GO in PBO matrix and covalent bonding networks at the interface between GO and PBO molecular chains. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Study on the thermal degradation of high performance fibers by TG/FTIR and Py-GC/MS

The thermal degradation behaviors of Kevlar 49, Kevlar 129 (Poly(p-phenylene terephthamide), Nomex (polyisophthaloyl metaphenylene diamine), and PBO(poly(p-phenylene benzobisoxazole)) fibers were measured by TG/FTIR and Py-GC/MS. The characteristic temperatures of the fibers in air were obtained by TG. It indicated that the initial degradation temperature of the PBO is the highest. The initial degradation temperature of Nomex fiber is the lowest, but the end decomposition temperature of Nomex is the highest. The gases released by the pyrolysis in air were mainly CO₂, CO, H₂O, NO, and HCN, also containing a small amount of NH₃, and the absorption peaks of CO₂ were the strongest. The results of Py-GC/MS showed that CO₂ and benzene were the most pyrolysis fragment. With the change of pyrolysis temperature, the chromatogram and mass spectra results take a large variety. The pyrolysates can help us to study the pyrolysis process of high performance fibers.     

抗紫外老化聚对苯撑苯并二噁唑(PBO)纤维的制备与表征

通过化学添加2,5-二羟基对苯二甲酸(DHTA)共聚,以及添加金红石型纳米TiO2物理共混的方法,制备了聚对苯撑苯并二噁唑(PBO)的抗紫外改性纤维.考察了纤维的力学性能、特性粘度及表面形貌在紫外老化过程中的变化,并结合PBO纤维紫外加速老化后的红外分析,对PBO纤维的光老化机理进行了初步研究.结果表明,本实验所制备的DHPBO纤维以及DHPBO/n-TiO2纤维的抗紫外老化能力明显高于PBO纤维,并且金红石型纳米TiO2对PBO的抗紫外改性效果要优于有机紫外吸收剂(2,2'-(1,2-乙烷二基)双(4,1-亚苯基)双苯并噁唑).     

苯并二噁唑系列聚合物的合成及表征

以4,6-二氨基-1,3-苯二酚盐酸盐为原料,分别和对苯二甲酸、1,4-萘二甲酸、2,6-萘二甲酸、2,5-噻吩二甲酸、4,4-′(1,2-二苯基乙烯)二甲酸在多聚磷酸介质中反应,合成单环的聚(1,4-亚苯基)苯并二噁唑(PBO)、稠环的聚(1,4-亚萘基)苯并二噁唑(1,4-PNBO)和聚(2,6-亚萘基)苯并二噁唑(2,6-PNBO)、杂环的聚(2,5-亚噻吩基)苯并二噁唑(PTBO)及含有两个苯环的聚-4,4′-亚(1,2-二苯乙烯基)苯并二噁唑(4,4′-PDPEBO).采用傅立叶红外光谱、热重分析、元素分析、特性黏数分析对系列聚合物进行了表征.研究结果表明PBO、1,4-PNBO、4,4-′PDPEBO、2,6-PNBO和PTBO 5种聚合物的耐热性能依次降低,特性黏数依次为25.40、16.76、20.63、15.38和14.63 dL/g.     

Resonance raman spectra of poly‐(p‐phenylenebenzobisoxazole), poly‐(p‐phenylenebenzobisthiazole), and poly(pyridobisimidazole)

Resonance Raman spectra of poly(p‐phenylenebenzobisoxazole) (PBO), poly(p‐phenylenebenzobisthazole) (PBZT), and poly(pyridobisimidazole) (PIPD) were measured. In the case of PBO, no large dependence on wavelength of excited laser can be observed, whereas in the cases of PBZT and PIPD, the spectra depends on wavelength of excited laser. This difference may be attributed to the colors of the samples: PBO is gold, and PBZT and PIPD are metallic blue, which show the different conjugated states. The spectra of PBO are rather simpler than those of PBZT and PIPD. This is considered to be reflected by the fact that only a chain passes through the unit cell of PBO, while two chains pass through the unit cell of PBZT and PIPD. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1791–1793, 2001     

Synthesis and Characterization of Poly(N-isopropylacrylamide) and Poly(vinyl acetate) Diblock Copolymers via MADIX Process

The synthesis of diblock copolymers of poly(N-isopropylacrylamide) (PNIPAM) and poly(vinyl acetate) (PVAc) was performed by macromolecular design via interchange of xanthates (MADIX) process. Following the preparation of methyl (isopropoxycarbonothioyl) sulfanyl acetate (MIPCTSA) as chain transfer agent, it was reacted with vinyl acetate to obtain PVAc macro-chain transfer agent. Then, block copolymerization was completed by successive addition of N-isopropylacrylamide (NIPAM). ¹H NMR spectroscopy confirmed the presence of both blocks in the copolymer structure, with the expected composition based on the feed ratio. Size Exclusion Chromatography (SEC) was used to investigate the relative values of molecular characteristics. Only 20% of PVAc was converted to block copolymer. The resultant block copolymer structures were further examined in terms of their morphologies as well as critical micelle concentration (CMC) by using ESEM and Fluorescence Excitation Spectroscopic techniques, respectively. Morphological characterization confirmed amphiphilic block copolymer formation with the existence of mainly ca. 100 nm well distributed micelles. The thermo responsive amphiphilic behavior of the block copolymer solutions were followed by Dynamic Light Scattering (DLS) technique.     

Synthesis and Characterization of Amphiphilic Poly(caprolactone) Star Block Copolymers

Summary: Novel, star‐shaped, amphiphilic block copolymers composed of fully degradable poly(caprolactone) were synthesized by sequential addition polymerization. In the first step, four‐arm macroinitiators were produced by ring‐opening polymerization of caprolactone by initiation with pentaerythritol. Then, block copolymers were synthesized by sequential addition of 4‐(2‐benzyloxyethyl)‐ε‐caprolactone to the four‐arm macroinitiators. Star‐shaped, amphiphilic block copolymers containing poly(caprolactone)‐block‐poly[4‐(2‐hydroxyethyl)caprolactone] segments were obtained by catalytic debenzylation.

Four‐arm amphiphilic polycaprolactone star block copolymer.     

Linear and four‐armed poly(l‐lactide)‐block‐poly(d‐lactide) copolymers and their stereocomplexation with poly(lactide)s

Linear and four‐armed poly(l ‐lactide)‐block‐poly(d ‐lactide) (PLLA‐b‐PDLA) block copolymers are synthesized by ring‐opening polymerization of d ‐lactide on the end hydroxyl of linear and four‐armed PLLA prepolymers. DSC results indicate that the melting temperature and melting enthalpies of poly (lactide) stereocomplex in the copolymers are obviously lower than corresponding linear and four‐armed PLLA/PDLA blends. Compared with the four‐armed PLLA‐b‐PDLA copolymer, the similar linear PLLA‐b‐PDLA shows higher melting temperature (212.3 °C) and larger melting enthalpy (70.6 J g^?1). After these copolymers blend with additional neat PLAs, DSC, and WAXD results show that the stereocomplex formation between free PLA molecular chain and enantiomeric PLA block is the major stereocomplex formation. In the linear copolymer/linear PLA blends, the stereocomplex crystallites (sc) as well as homochiral crystallites (hc) form in the copolymer/PLA cast films. However, in the four‐armed copolymer/linear PLA blends, both sc and hc develop in the four‐armed PLLA‐b‐PDLA/PDLA specimen, which means that the stereocomplexation mainly forms between free PDLA molecule and the inside PLLA block, and the outside PDLA block could form some microcrystallites. Although the melting enthalpies of stereocomplexes in the blends are smaller than that of neat copolymers, only two‐thirds of the molecular chains participate in the stereocomplex formation, and the crystallization efficiency strengthens. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1560–1567     

苯并双噁唑类聚合物的合成

详细介绍了以4,6-二氨基间苯二酚盐酸盐(DADHB)为原料,采用多聚磷酸法、三甲基硅烷基化法、中间相聚合法、单体成盐法合成聚对苯撑苯并双噁唑(PBO),还有以4,6-二硝基间苯二酚(DNR)为原料,先选择还原制得4-氨基-6-硝基间苯二酚盐酸盐,进而与对甲氧羰基苯甲酰氯进行缩环合获得苯并噁唑化合物,再催化加氢合成AB型PBO新单体2-(对甲氧羰基苯基)-5-氨基-6-羟基苯并噁唑,最后自缩聚反应制备PBO的新路线.另外,本文还介绍了直链烯烃型、直链脂肪烷烃型、稠环芳烃型、联苯取代基型、杂环型、聚醚型等苯并双噁唑类聚合物的合成方法.     

Porosity development in chars from thermal degradation of poly(p-phenylene benzobisoxazole)

The main objective of this work was to investigate porosity development in carbonaceous materials formed by thermal degradation of the high thermal stability polymer, poly(p-phenylene benzobisoxazole) (PBO). Two varieties of PBO, as-spun (AS) and high-modulus (HM) were studied. Chars obtained at various polymer decomposition temperatures (selected on the basis of thermogravimetric and differential thermal analysis results) were characterized by elemental analysis, infrared spectroscopy, X-ray diffraction and CO₂ adsorption at 273 K. The obtained adsorbents essentially contained narrow micropores, and maximum pore development took place at ca. 1000 K, when the polymer was not yet completely decomposed. At higher temperatures, there is a certain pore widening along with a displacement towards smaller pore sizes, and the pore volume significantly decreases.     

Poly(p‐phenylene methylene)‐based block copolymers by mechanistic transformation

The synthesis of poly(p‐phenylene methylene) (PPM)‐based block copolymers such as poly(p‐phenylene methylene)‐b‐poly(ε‐caprolactone) and poly(p‐phenylene methylene)‐b‐polytetrahydrofuran by mechanistic transformation was described. First, precursor PPM was synthesized by acid‐catalyzed polymerization of tribenzylborate at 16 °C. Then, this polymer was used as macroinitiators in either ring‐opening polymerization of ε‐caprolactone or cationic ring‐opening polymerization of tetrahydrofuran to yield respective block copolymers. The structures of the prepolymer and block copolymers were characterized by GPC and ¹H NMR investigations. The composition of block copolymers as determined by ¹H NMR and TGA analysis was found to be in very good agreement. The thermal behavior and surface morphology of the copolymers were also investigated, respectively, by differential scanning calorimetry and atomic force microscopy measurements, and the contribution of the major soft segment has been observed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Annealing effect on performance and morphology of photovoltaic devices based on poly(3‐hexylthiophene)‐b‐poly(ethylene oxide)

Novel block copolymers, poly(3‐hexylthiophene)‐b‐poly(ethylene oxide) (P3HT‐b‐PEO) were synthesized via Suzuki coupling reaction of P3HT and PEO homopolymers. The copolymers were characterized by NMR, gel permeation chromatography, differential scanning calorimeter, and UV–vis measurements. A series of devices based on the block copolymers with a fullerene derivative were evaluated after thermal or solvent annealing. The device using P3HT‐b‐PEO showed higher efficiency than using P3HT blend after thermal annealing. Phase‐separated structures in the thin films of block copolymer blends were investigated by atomic force microscopy to clarify the relationship between morphologies constructed by annealing and the device performance. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis of organic–inorganic chiral block poly(methylphenylsilane) functional polymers,and study of their optical and chiroptical properties

Polysilanes upon UV irradiation give rise to silyl macroradicals which are capable to initiate radical polymerization. Hence, chiral block functional polysilanes were synthesized by UV irradiation of poly(methylphenylsilane) (PMPS) with a vinyl chiral monomer, (R)‐N‐(1‐phenylethyl)methacrylamide (R‐NPEMAM). The synthesized copolymer samples were characterized by FTIR, NMR, and UV–vis spectroscopy. The number and weight average molecular weights of PMPS and synthesized chiral‐block‐PMPS were measured by GPC analysis. Two glass transition temperatures (T_g) of the synthesized materials clearly indicate the formation of chiral‐block‐PMPS copolymers. SEM analysis also indicated the synthesized organic–inorganic block copolymers. The optical and chiroptical properties of the synthesized materials were studied. The cotton effect is observed not only at 276 nm due to aromatic ring of the chiral monomer units but also at 325 nm which is associated with the Si–Si conjugation of PMPS block of synthesized functional polysilanes. Such tunable chirality may find potential application in optoelectronics. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3626–3634     

Aging behavior of PBO fibers and PBO‐fiber‐reinforced PPESK composite after oxygen plasma treatment

Aging behavior of poly(p‐phenylene benzobisoxazole) (PBO) fibers and PBO‐fiber‐reinforced poly(phthalazinone ether sulfone ketone) (PPESK) composites after oxygen plasma treatment was investigated. Surface chemical composition, surface roughness and surface morphologies of oxygen‐plasma‐treated PBO fibers before and after aging in air for 1, 3, 5 and 10 days were analyzed by XPS and atomic force microscopy (AFM). The effects of aging on the material were examined by interlaminar shear strength (ILSS) and water absorption measurements. The results indicate that the major aging behavior of the fibers and the composite appeared in the first few days after oxygen plasma treatment, whereas minor aging effects were observed with prolonged aging. Copyright © 2008 John Wiley & Sons, Ltd.     

Poly(2-oxazoline)-Based Polyplexes as a PEG-Free Plasmid DNA Delivery Platform

The present study expands the versatility of cationic poly(2-oxazoline) (POx) copolymers as a polyethylene glycol (PEG)-free platform for gene delivery to immune cells, such as monocytes and macrophages. Several block copolymers are developed by varying nonionic hydrophilic blocks (poly(2-methyl-2-oxazoline) (pMeOx) or poly(2-ethyl-2-oxazoline) (pEtOx), cationic blocks, and an optional hydrophobic block (poly(2-isopropyl-2-oxazoline) (iPrOx). The cationic blocks are produced by side chain modification of 2-methoxy-carboxyethyl-2-oxazoline (MestOx) block precursor with diethylenetriamine (DET) or tris(2-aminoethyl)amine (TREN). For the attachment of a targeting ligand, mannose, azide-alkyne cycloaddition click chemistry methods are employed. Of the two cationic side chains, polyplexes made with DET-containing copolymers transfect macrophages significantly better than those made with TREN-based copolymer. Likewise, nontargeted pEtOx-based diblock copolymer is more active in cell transfection than pMeOx-based copolymer. The triblock copolymer with hydrophobic block iPrOx performs poorly compared to the diblock copolymer which lacks this additional block. Surprisingly, attachment of a mannose ligand to either copolymer is inhibitory for transfection. Despite similarities in size and design, mannosylated polyplexes result in lower cell internalization compared to nonmannosylated polyplexes. Thus, PEG-free, nontargeted DET-, and pEtOx-based diblock copolymer outperforms other studied structures in the transfection of macrophages and displays transfection levels comparable to GeneJuice, a commercial nonlipid transfection reagent.