The crystal structure of poly(4,4′‐diphenylsulfonyl terephthalamide) (pt‐PSA) is studied by X‐ray diffraction and molecular simulation. Although the number of observed reflections is limited to warrant a precise determination of the unit cell structure and symmetry, a reasonable monoclinic unit cell is suggested with dimensions of a = 0.645 nm, b = 0.488 nm, c = 3.010 nm, and γ = 122.5°. A twofold molecule with two monomeric units forming a large zigzag conformation satisfies the X‐ray diffraction data. A layer structure is formed in the crystal phase, which is stabilized by the hydrogen bond between ? NH and ? C?O and the parallel‐displaced π–π stacking from the distortional coplanarity of the benzene rings and amide group.
A series of highly branched star‐comb poly(ε‐caprolactone)‐block‐poly(l ‐lactide) (scPCL‐b‐PLLA) are successfully achieved using star‐shaped hydroxylated polybutadiene as the macroinitiator by a simple “grafting from” strategy. The ration of each segment can be controlled by the feed ratio of comonomers. These star‐comb double crystalline copolymers are well‐defined and expected to illustrate the influences of the polymer chain topology by comparing with their counterparts in linear‐shaped, star‐shaped, and linear‐comb shape. The crystallization behaviors of PCL‐b‐PLLA copolymers with different architectures are investigated systematically by means of wide‐angle X‐ray diffraction, differential scanning calorimetry, and polarized optical microscopy analysis. It is shown that the comb branched architectures promote the crystallization behavior of each constituent significantly. Both crystallinity and melting temperature greatly raise from linear to comb‐shaped copolymers. Compared to linear‐comb topology, the star‐comb shape presents some steric hindrance of the graft points, which decrease the crystallinity of scPCL‐b‐PLLA. Effects of copolymer composition and chain topology on the crystallization are studied and discussed.
Improving fragility is important for the practical application of gels. In this study, the mechanical strength of gels composed of poly(N‐vinyl acetamide) (PNVA) and glycols is investigated focusing on the retained solvent in the gels. The solvent for the PNVA hydrogel is adequately replaced by various glycols. Using poly(ethylene glycol) (PEG) with molecular weights of 400 or 600 g mol?1, the compressive strength of the gel is dramatically enhanced to approximately 10 MPa while that of hydrogel is 0.2 MPa. This is because of solvent viscosity, interaction between PEG and PNVA, and the favorable aggregation of the PNVA. From FTIR spectroscopy investigations, the absorption bands of the carbonyl and amino groups of PNVA gels with PEG400 are shifted as compared with PNVA gels in water, suggesting hydrogen bond formation.
A series of novel segmented linear and crosslinked polyurethanes (PUs) are synthesized from poly(ε‐caprolactone) (PCL) (25 kg mol?1), methylene diphenyl diisocyanate (MDI), and various polyether diols (Pluronic (PLU) and polyethylene glycol (PEG)). The basic structures of the highly deformable PUs are PLU/PEG–MDI–PCL–MDI–PLU/PEG and PLU–MDI–PCL–MDI–PLU, respectively. The linear and crosslinked PUs are characterized. Changes in the tensile behavior are attributed to the effects of compositional variables and alterations in the crosslink density. Additional information on the morphology of the segmented PUs is deduced from differential scanning calorimetry, as well as transmission and scanning electron microscopy investigations. Both the linear and the crosslinked PUs exhibit a broad rubbery plateau above the melting temperature of the crystalline PCL phase, which is highly beneficial for shape memory function. This work highlights that the chemical build‐up of soft segments containing high‐molecular‐weight crystallizable chain units is a proper tool to tailor the morphology and mechanical properties of PUs, and thus also their shape memory properties.
Upper critical solution temperature (UCST)‐type thermoresponsive behavior of poly(ethylene glycol)–poly(acrylic acid) (PEG–PAA) and poly(poly(ethylene glycol) methacrylate)–poly(acrylic acid) (PPEGMA–PAA) interpolymer complexes has been observed in isopropanol. For these investigations, PPEGMA and PAA with various average molecular weights have been synthesized by atom transfer radical polymerization. It has been found that both the PEG and PPEGMA have lower cloud point temperatures (T cp) than its mixed polymer solutions with PAA, whereas PAA does not show such behavior in the investigated temperature range. These findings indicate the reversible formation of interpolymer complexes with variable structure and composition in the solutions of the polymer mixtures in isopropanol. Increasing the ethylene glycol/acrylic acid molar ratio or the molecular weight of either the PAA or the H‐acceptor PEG component of the interpolymer complexes increases the UCST‐type cloud point temperatures of these interpolymer systems. The polymer–polymer interactions by hydrogen bonds between PAA and PEG or PPEGMA and the correlations between T cp and structural parameters of the components revealed in the course of these investigations may be utilized for exploring well‐defined UCST‐type material systems for various applications.
A two‐step synthesis of high‐molecular‐weight and bio‐based poly(butylene succinate) (PBS) from succinic anhydride and butane‐1,4‐diol is established, in which the first step is a 12 h atmospheric polycondensation at 95 °C in the presence of succinic acid. The subsequent polymerization, catalyzed by Novozym 435 suspended in toluene, yields PBS with a molecular weight above 73 000 g mol?1. The recovered lipase catalyst appears to give similar performance after six cycles. The versatility of this atmospheric synthetic route to PBS copolymers is validated through the syntheses of poly(butylene succinate‐co‐butylene malate) (PBSM), poly(butylene succinate‐co‐butylene fumarate) (PBSF), and poly(butylene succinate‐co‐butylene terephthalate) (PBST), in which succinic acid is replaced by corresponding di‐acids as monomers.
The new aluminum compounds 1–3 modified by unsaturated alcohol, Me3−nAl(O(CH2)4OCHCH2)n (n = 1 ( 1 ), 2 ( 2 ), 3 ( 3 )), are synthesized and investigated by multinuclear (1H, 13C, 27Al) NMR spectroscopy. The compounds 1 – 3 initiate living ring‐opening polymerization of ε‐caprolactone in bulk at 40–80 °C to afford polyesters with controlled molecular weight (M n up to 35 000 g mol−1) and relatively narrow molecular weight distribution (M w/M n < 1.8). Among initiators studied here, aluminum trialkoxide shows the highest activity, whereas aluminum dialkoxide is a less active. In all cases, the fragment of unsaturated alcohol is transferred to the end of the polymeric chain with high degree of functionality (>85%) yielding macromonomers. These macromonomers are copolymerized with maleic anhydride to give poly(vinyl ether‐co‐maleic anhydride)‐g‐poly(ε‐caprolactone) graft copolymers.
Molecular‐recognition‐responsive characteristics of a novel poly(N‐isopropylacrylamide‐co‐benzo‐12‐crown‐4‐acrylamide) (PNB12C4) hydrogel have been investigated. In the prepared PNB12C4 hydrogel, benzo‐12‐crown‐4 (B12C4) groups act as guest molecules and γ‐cyclodextrin (γ‐CD)‐receptors, and poly(N‐isopropylacrylamide) (PNIPAM) networks act as phase‐transition actuators. The formation of stable γ‐CD/B12C4 complexes enhances the hydrophilicity of the PNB12C4 hydrogel networks, and induces positive shift of the volume phase transition temperature (VPTT) of PNB12C4 hydrogel. Moreover, the PNB12C4 hydrogel also shows thermoresponsive adsorption property selectively towards γ‐CD. The γ‐CD‐recognition sensitivity of PNB12C4 hydrogel can be dramatically improved by increasing γ‐CD concentration in solution or B12C4 content in PNB12C4 copolymer networks. The results in this study provide valuable information for developing crown ether‐based smart materials in various applications.
A series of ZrIV and TiIV complexes containing the 6‐(2‐(diethylboryl)phenyl)pyridyl‐2‐yl motif are used in the methylalumoxane‐triggered copolymerization of ethylene (E) with norborn‐2‐ene (NBE). 13C NMR analyses reveal that vinyl insertion polymerization (VIP)‐derived poly(E)‐co‐poly(NBE) is obtained with pre‐catalysts 1–4 and 6 , while pre‐catalyst 5 allows for the synthesis of a copolymer that contains both VIP‐ and ring‐opening metathesis polymerization (ROMP)‐derived structures. All the VIP‐derived poly(E)‐co‐poly(NBE) sequences show predominantly isolated NBE/alternating‐syndiotactic E‐NBE, as well as alternating‐isotactic E‐NBE sequences. The microstructure of the copolymers is correlated with the propensity of the pre‐catalysts to allow tandem ROMP‐VIP.
Lamellar bending habits, as influenced by molecular‐chain chirality, in packing into dendritic spherulites with specific optical patterns are discussed using two model polymers of opposite chirality that are blended with a common polymer as examples: i) poly(l ‐lactic acid)/poly(butylene adipate) (PLLA/PBA) and ii) poly(d ‐lactic acid)/PBA (PDLA/PBA) blends. The bending habits in the spherulites of PLLA or PDLA blended with PBA are dictated by the chirality, specifically the counterclockwise and clockwise directions for the PLLA/PBA (50:50) and PDLA/PBA (50:50) blends, respectively. Straight lamellae in spiral lozenge crystals are packed with crystal aggregates of PLLA on top of the flat‐on lamellae plates acting as a basal plane during crystallization at Tc; spiral lozenge‐crystal frameworks are surrounded by needle‐like crystals resembling PBA crystals.
Highly sensitive and selective detection of morphine is exhibited using a capacitive transducer coated with cathodically electropolymerized and molecularly imprinted poly(p aminostyrene). Through molecular imprinting, morphine‐specific recognition sites have been fabricated throughout the film, which shows exceptional binding activity toward morphine based from electrochemical capacitance measurements. The thin film sensor has a linear response to morphine solutions with 20–40 × 10?6 m concentrations and a detection limit of 5.95 × 10?6 m . It demonstrates high selectivity toward morphine as compared to other analog molecules including nicotine and cholesterol. The formation of the polymer film is facilitated and monitored using electrochemical‐quartz crystal microbalance and characterized by X‐ray photoelectron spectroscopy. Infrared spectroscopy confirms the loading and removal of the analyte from the film. Based on molecular modeling calculations, strong hydrogen‐bonding interactions between the monomer, cross‐linker, and analyte form a stable pre‐polymerization complex, which is critical in successfully imprinting morphine into the film and effective sensing of the analyte.
In this work, an agarose/poly(acrylamide‐co‐acrylic acid) interpenetrating network hydrogel is prepared by the photopolymerization of acrylamide, acrylic acid, and N ,N ′‐methylenebisacrylamide within agarose network at its gel state. The as‐prepared hydrogel exhibits two independent kinds of shape memory effects. The thermal‐activated shape memory behavior is attributed to the reversible coil‐helix transformation of agarose, within the permanently cross‐linked poly(acrylamide‐co‐acrylic acid) network; the light triggered shape recovery is driven by the dissociation of the complexes between carboxyl groups and Fe(III) ions, due to the photoreduction of Fe(III) to Fe(II) in the presence of citric acid. The versatile and simple strategy as presented here should be beneficial for the design of dual‐activated shape memory hydrogels and foster their use in a number of fields such as biomaterials, soft robotics, smart actuators, and sensors.
Star‐shaped poly(2‐isopropyl‐2‐oxazolines) with dramatically hydrophobic dendrimer core are synthesized using carbosilane dendrimers of first to third generations as macroinitiators. It is observed that half of the initiator functional groups are incorporated in polymerization process. The polymerization degree of polyoxazoline arms is about 25. Strong arm folding results in small molecule dimensions in both aqueous and organic solutions. Thermosensitive properties are studied for second generation‐based star solution with the concentration of 0.00095 g cm−3. Model linear poly(2‐isopropyl‐2‐oxazolines) are investigated for comparison. Carbosilane dendrimer core interaction leads to the formation of different types of aggregates at low temperatures. The temperatures of the beginning (T 1 = 42–43 °C) and finishing (T 2 = 50 °C) of phase separation are determined. It is shown that macromolecule compactization and aggregation take place even far from the phase transition interval and alternately prevail on heating.
Dendrigraft poly(l ‐lysine) (DGL) polyelectrolytes, obtained by iterative polycondensation of N‐trifluoroacetyl‐l ‐lysine‐N‐carboxyanhydride, constitute very promising candidates in many biomedical applications. In order to get a better understanding of their structure–property relationships in these applications, their absolute average molecular weights have to be accurately measured. Size‐exclusion chromatography coupled to a multi‐angle laser‐light‐scattering detector (SEC‐MALLS) is known to be the most appropriate analytical tool. These measurements require the determination of the refractive index increment, dn/dc, of these highly branched polycationic macromolecules in aqueous solution. This optical property has to be measured in the same aqueous conditions as SEC‐MALLS eluents. Consequently, data are determined and discussed as a function of different aqueous SEC‐MALLS eluents, as well as different counter‐ions of the many ammonium groups of DGL (generation 3, DGL‐3, used as a model herein). The resulting number‐average molecular weights, , are found to be very dissimilar when the measured dn/dc values are directly considered. In contrast, very close values are obtained (average = 18 700, standard error of 1110 g mol?1) with a low coefficient of variation for such data (ca. 6% for six analyses), when the dn/dc are corrected by the exact lysine amount (measured by the total Kjeldahl nitrogen method).
The Janus polymerization combines cationic and anionic polymerizations into growing chains with two different chain ends. This provides a novel pathway to produce topologically interesting polymers. Here this polymerization is applied to allow the synthesis of branched polytetrahydrofuran (bPTHF) and poly(tetrahydrofuran‐co‐ε‐caprolactone) (bPTC). Rare earth triflates [RE(OTf)3] (RE = Lu, Sc, and Y) are used as catalyst, and small amounts (0.10–0.15 mol%) of ethylene glycol diglycidyl ether act as both initiator and comonomer due to the different reactivities of the two epoxide groups. The poly(ε‐caprolactone) block in bPTC provides crystalline domains and potential degradation under acidic conditions. The products of bPTHF show unusual tensile properties with a high strain at break of 1070% differing greatly from linear PTHF. Due to the large number of terminal hydroxyl groups and their strong hydrogen bonding, bPTHF has self‐healing properties with potentially promising applications.
This study reports the synthesis and characterization of poly(3‐hexylthiophene) (P3HT) from a direct heteroarylation polymerization of two isomeric monomers, 2‐bromo‐3‐hexylthiophene (monomer 1 ) and 2‐bromo‐4‐hexylthiophene (monomer 2 ). Using the Herrmann–Beller catalyst along with P(o‐NMe2Ph)3, the resulting polymers are obtained in excellent yields and exhibit a good number‐average molecular weight (Mn of 33 and 16 kDa, respectively). Detailed 1H NMR analyses reveal less than 1% of homocouplings and no evidence of β‐branching. Dehalogenation is identified as the main chain termination step and preferentially occurs on monomer 2 . The melting temperature (237 °C) and hole mobility (up to 0.19 cm2 V?1.s?1) of the nearly defect‐free P3HT obtained from this simple polymerization of monomer 1 are comparable, if not superior, to those obtained with commercially available GRIM and Rieke samples.
A perylene bisimide derivative of N,N′‐diisopropylphenyl‐1,6,7,12‐tetrachloroperylene‐3,4,9,10‐tetracarboxyl bisimide (PBI) is synthesized and used as a sensitizer for a photorefractive (PR) polymer composite. Small amount (0.1 wt%) of PBI sensitizer gives the maximum PR performance of composite based on poly(4‐(diphenylamino)benzyl acrylate) (PDAA) (45 wt%), 2‐(4‐(azepan‐1‐yl)benzylidene)malononitrile (35 wt%), and (4‐(diphenylamino)phenyl)methanol (24.9 wt%). High external diffraction efficiency of 49%, response time of 47 ms, and sensitivity of 28 cm2 J?1 are obtained under an applied electric field of 40 V μm?1 at writing beam of 532 nm. PBI sensitizer effectively forms a charge‐transfer complex with PDAA, which favors the generation of the charge carriers followed by the space‐charge formation. Furthermore, low PBI concentration contributes to low absorption coefficient at 532 nm, which leads to better PR performance.
The radical copolymerization of N‐substituted maleimides containing polymethylene and poly(ethylene oxide) side chains as the N‐substituent groups with isobutene, styrene, and α‐methylstyrene as the electron‐donating monomers is carried out in order to investigate the structure and thermal properties of the resulting comb‐like copolymers. The obtained copolymers show excellent thermal stability and their glass transition temperatures vary depending on the chain length of the introduced N‐substituents. The main‐ and side‐chain motions of the copolymers are investigated by dynamic mechanical analysis at various frequencies over the temperature range of ?150 to 100 °C.
Graft polymers with poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) as backbones are successfully prepared via two convenient steps. The utilization of semiflexible PPO as backbones offers unique properties for the graft polymers. Thermal, rheological, and phase behaviors of these new graft polymers are well controlled via the precise design of architectural parameters. The disordered microphase separation in melt state and the proper composition of side grafts provide the ease of thermal processing for these graft polymers. The graft density shows impact on the relaxation and mechanical properties of the thermoplastics. This work shows the possibility to use lots of semiflexible engineering polymers as backbones to construct new thermoplastics.
In this paper, “star anise”‐like anisotropic micelle (AM) from direct aqueous self‐assembly of poly(ethylene oxide)‐block‐poly(p‐dioxanone) amphiphilic diblock copolymer is presented. By adding poly(ethylene imine) (PEI), the AM shows morphological change from “star anise” to swollen sphere. The mechanism of PEI‐triggered morphological transition involving complexation and weakening of crystallizability is revealed.
下载免费PDF全文