Three novel photochromic azobenzene‐containing comb‐shaped polyacrylates are synthesized and their phase behavior and photo‐optical properties are studied. The influence of the side photochromic group structure, thermal treatment, and light irradiation on aggregation of azobenzene chromophores in thin spin‐coated films of the polymers is investigated in detail. Special attention is paid to studying the photo‐orientation processes in polymers films induced by polarized blue light (473 nm). The relationship between the photochromic group architecture, phase behavior, thermal treatment of films, and kinetics of chromophore photo‐orientation is established and discussed. It is found that the position of the N?N bond in chromophores plays an important role in the kinetics of the process, but does not affect the maximum value of dichroism.
Three polythiophenes with 5%, 10% and 15% triphenylamine trivinylene (TPAV) as bridge linker, PT‐TPAV5, PT‐TPAV10 and PT‐TPAV15, were synthesized. The Wittig‐Horner‐Emmons reaction and the Stille method were employed to synthesize these polymers. The polythiophenes were subsequently used in bulk‐heterojunction polymer solar cells (PSCs) as donor materials. The polymers exhibited a striking and reversible color change after the oxidation of the polymer films. The power conversion efficiencies of the PSCs based on PT‐TPAV5, PT‐TPAV10 and PT‐TPAV15 as donors and PCBM as acceptor were 0.17%, 0.50%, and 0.35%, respectively, under the illumination of AM 1.5, 100 mW · cm?2.
This study deals with the preparation of polyurethane‐graft‐poly(n‐butyl acrylate)s copolymers by polymerization of diphenyl‐methane‐4,4‐di‐isocyanate (MDI) with α,α′‐di‐hydroxyl‐poly(n‐butyl acrylate)s of different sizes as macromonomers. The polyaddition has been studied on the basis of kinetic measurements, and the comb‐like structure of the resulting polymer has been well‐established. Such grafted copolymers display specific adhesive properties in connection with their comb‐like architecture.
Summary: Starting in the 1960s, several kinds of photodeformable polymers have been developed, such as monolayers, polymer gels, solid films and liquid‐crystalline elastomers with different photodeformation mechanisms. This field evolved slowly until recently when significant achievements have been made. Most recently, Lendlein and co‐workers have put forward another new concept – using photo‐crosslinking to prepare deformable polymers with various pre‐determined shapes (Nature 2005 , 434, 879). This highlight gives a general introduction into photodeformable polymers and brings forth future challenges.
A polymer film doped with SCAA molecules where (a) is the permanent shape, (b) is the temporary shape and (c) is the recovered shape. 相似文献
Poly(ethylene azelate) (PEAz) was synthesized and its melting behavior was studied with DSC and Step Scan DSC. The equilibrium melting point of PEAz was found 62 °C and the heat of fusion of 100% crystalline polymer was estimated at 160 J · g?1. Polarized light microscopy showed mixed birefringence. From isothermal crystallization DSC study, after self‐nucleation, crystallization rates were estimated. The Lauritzen–Hoffman plots showed crystallization regime I to II and II to III transition at 34 and 19 °C respectively. Non‐isothermal crystallization was studied. The activation energy was calculated applying the isoconversional method of Friedman. Chemical hydrolysis of PEAz was very slow, while enzymatic hydrolysis showed comparable rates with PCL.
A new diblock copolymer composed of a regioregular block of poly[3‐[2‐(2‐methoxyethoxy)ethoxy]methylthiophene], bearing as side‐chain a hydrophilic substituent, and a regioregular block of poly[3‐(1‐octyloxy)thiophene], is prepared and characterized. The properties are compared with those of a related copolymer composed of poly(3‐hexylthiophene) and poly(3‐alkoxythiophene) blocks. The solvatochromic properties of these materials in solution are investigated by absorption and emission spectroscopy upon gradual addition of a poor solvent, and compared with those of the parent regioregular homopolymers. The experimental results are interpreted in terms of electronic interactions between the blocks. It is found that the different hydrophilicity of the side chain plays a crucial role for the electronic communication between blocks in poly(3‐alkylthiophene)‐block‐poly(3‐alkoxythiophene) copolymers.
Summary: A new thin‐film characterization setup was created based on the combination of a surface plasmon spectrometer with an electrochemical cell operated under high pressure of up to 200 MPa and at temperatures up to 120 °C. The examples given to document its performance include photoisomerization studies with poly(methyl methacrylate) (PMMA) films partly derivatized with disperse red (DR1), as well as, a preliminary account of the electropolymerization of EDOT under pressure and the assessment of the redox properties of the resulting thin PEDOT films.
Sketch of the high‐pressure electrochemistry surface plasmon cell. 相似文献
This paper reports the preparation of inclusion complexes of amylose with synthetic polymers by means of enzymatic polymerization of α‐D ‐glucose 1‐phosphate monomer (Glc‐1‐P). The synthetic polymers, employed as the guests, are poly(ε‐caprolactone), poly(δ‐valerolactone), and poly(ester‐ether), containing ester groups in the main chains. The formation of the inclusion complexes was carried out by the enzymatic polymerization of Glc‐1‐P catalyzed by phosphorylase in the presence of the guest polymers.
Summary: Here we report about the synthesis of colloidal particles of nematic and smectic liquid‐crystalline polymers. For this purpose mesogen‐containing acrylate monomers were synthesized and polymerized in a special modification of a precipitation polymerization called dispersion polymerization. By variation of the polymerization conditions colloidal particles of different size and polydispersity could be obtained including very narrowly distributed samples in optimized batches. On azobenzene‐containing colloidal particles switching experiments with polarized light were performed. It could be observed that the nematic director of the mesogens within the colloidal particles can be rotated due to the photochemical trans‐cis‐isomerization of the azobenzene chromophores.
The present article briefly reviews research developments in the area of biomacromolecules and bio‐related macromolecules, whose research papers have been published for several decades preferably in the Macromolecular Journals. The area covers the important classes of macromolecules, polysaccharides (cellulose, amylose, chitin, etc.), polyesters (poly(lactic acid), poly(hydroxyalkanoate)s, etc.), and phenolic polymers (lignin, urushi, etc.). These polymers and their derivatives are very important for scientific interests as well as for industrial applications. Their synthesis, structure, reactions, and properties are mainly mentioned, and important topics of the target polymers are selected and mostly chronologically reviewed.
Summary: After the condensation polymerization of benzoguanamine (BGA) and pyromellitic dianhydride (PMDA) under microwave irradiation, the resulting p‐π conjugate poly(amic acid) was grafted via the azo coupling reaction. The obtained side‐chain polymers were further grafted with TDI‐aliphatic alcohol derivatives and TDI‐aniline derivatives. The third‐order NLO coefficient and response time of PAA and graft polymers were measured by degenerated four wave mixing (DFWM) technique and their fluorescent properties were also investigated. All of the graft polymers have larger NLO coefficients and film‐formability than PAA. Their fluorescent properties were also changed by the different electronic effect of the side‐chains. The influences of the introduction of side‐chains, the side‐chain length and the electronic effect of the substituting groups on the azobenzol side‐chain to both optical properties of the polymers by varying the conjugation degree were investigated.
A series of polynorbornene homo‐ and copolymers containing aryl‐ and/or hetaryl‐azo dyes were prepared through ring‐opening metathesis polymerization (ROMP). Thermal studies indicated that the polymers were thermally stable up to 250 °C, and possessed glass transition temperatures ranging from 93 to 133 °C. In THF solutions, the aryl‐azo dye containing homopolymers, displayed λmax = 417 nm while the hetaryl‐azo dye containing homopolymers displayed λmax = 495 nm. The copolymers displayed a λmax that encompassed both the aryl‐ and hetaryl‐azo dye range. The monomers and polymers showed bathochromic shifts in solution when acidified. The polymers were cast into films that changed colour in the presence of both aqueous 1.2 M HCl or HCl(g). The colour change reverses when exposed to aqueous 1.2 M NaOH or NH3(g). This process was repeated several times without disintegration of the polymer film, indicating that these polymers may be useful as reusable acid sensors.
It is now evident that ADMET chemistry can be employed to prepare a family of unsaturated carbosilane polymers containing a common backbone decorated with different alkoxysilane pendant groups, demonstrating the generality and potential utility of this chemistry. Four functionalized silicon containing dienes have been synthesized by nucleophilic substitution of the same parent diene monomer containing two reactive silicon‐chlorine bonds. These new α,ω‐diene monomers have been polymerized under ADMET conditions using the 2nd generation Grubbs's ruthenium catalyst, producing polymers with useful molecular weights. Variation of the pendant group results in differing chemical and physical properties of the resulting polymers. We believe this chemistry offers much to broaden the synthetic pathways to new organosilicon polymers.
Summary: New monomeric benzo[de]isoquinoline‐1,3‐dione blue emitting fluorophores, containing hindered amine stabilizer fragment have been synthesized under phase transfer catalysis conditions and their ability for “one‐step” optical bleaching and stabilization of poly(methyl methacrylate) has been demonstrated. During the co‐polymerization, no changes in the chromophoric system of the fluorophore occurred. The chemical bonding of the synthesized monomers in the polymer chain was confirmed spectrophotometrically. The absorption and some basic photophysical characteristics of the low and high molecular weight fluorescent brighteners have been determined. Photostability of the new monomeric fluorophores and their influence on the photostability of the blue emitting side‐group co‐polymers obtained have been established. A significant stabilizing effect against photodegradation was determined.
Summary: A novel bisphenol, (4‐chloro‐3‐trifluoromethyl)phenylhydroquinone (3FC‐PH), was synthesized via a three‐step synthetic procedure. Four aromatic polyethers based on 3FC‐PH were prepared via a nucleophilic aromatic substitution polycondensation. These polymers had a high thermal stability, and the temperatures at a 5% weight loss were above 516 °C in air. The solubility of the polyethers was improved by the introduction of bulky pendant groups. The average refractive indices of the polymer films at 1 320 nm were in the range 1.5381–1.6145. The dielectric constants of the polyether films estimated from the refractive indices were 2.69–2.98. Highly fluorinated 3FC‐PAE exhibited lower light absorption in the near‐IR region.
Direct visualization of crystal growth in poly(L ‐lactide) thin films was carried out by using a temperature‐controlled atomic force microscopy (AFM). At the initial stage of crystallization, edge‐on lamellar crystals have nucleated and elongated. Subsequently, the edge‐on lamellar crystals showed S‐shaped morphology and changed their orientation from edge‐on manner to flat‐on one. The curvature of edge‐on lamellar crystal has been discussed in terms of inclination and distortion of polymer chains in the crystal. In addition, mechanism on the formation of flat‐on crystal from edge‐on lamellae was proposed as derivative growth on the basis of in situ AFM observation of crystal growth and enzymatic degradation.
Multiarm PEO star polymers with a purely aliphatic polyether structure have been synthesized using hyperbranched polyglycerol (PG) with different molecular weights as a multifunctional initiator. Different degrees of deprotonation of the initiator were studied with respect to molecular weight control. The results show that the degree of deprotonation is a crucial parameter for the synthesis of well‐defined polymers with controlled molecular weights. Partial deprotonation of the PG hydroxyl groups (5–8%) was proven to represent an optimum for the synthesis of star polymers with molecular masses close to the theoretical values. Molecular weights of the stars ranged between 9 000 and 30 000 g · mol?1. MALDI‐ToF spectra confirmed that the PEO arms in the star polymers possess homogeneous lengths.
The aggregation of polyhedral oligomeric silsesquioxane (POSS) in copolymers was studied by incorporation of POSS into fluorinated copolymers, namely poly(octafluoropentyl acrylate) elastomers. The aggregation of POSS in copolymers affords unique materials. Studies of these novel polymers show POSS aggregates in these copolymers with both the phenyl and isobutyl peripheries, as the chain‐repulsive fluorinated chains help drive this aggregation. The isooctylPOSS copolymers, however, do not have POSS aggregation. Thermal studies of these copolymers also show an increase in the decomposition temperature by incorporation of POSS, which is directly dependent on the POSS periphery.
We report on the first examples of the free radical polymerization of a fluorinated 2‐vinylcyclopropane 1 and its copolymerization with an alkyl 2‐vinylcyclopropane 2 in aqueous solution via their host‐guest complexation with a random methylated β‐cyclodextrin (RAMEB) using a water‐soluble initiator (VA50). Upon polymerization, the dethreaded cyclodextrin remained in water solution, whereas the water‐insoluble polymer precipitated out and was isolated. The polymers prepared exhibited mesophase behavior over a wide range of temperature. Both Tg and Ti of the copolymers increased linearly with the amount of fluorinated co‐units.
Complexation of fluorinated vinylcyclopropane 1 with RAMEB and polymerization in water solution. 相似文献
The degradation of low‐MW ( = 1 500 g · mol?1) model compounds of pBA and pHEMA were studied under conditions corresponding to the worst‐case temperatures and irradiation intensities likely to be experienced by a surface coating exposed to the harsh Australian environment. Vinyl‐terminated polymers were compared to their saturated analogues; the terminal vinyl bond was found to be a source of instability which rendered the polymers more susceptible to degradation. The cyclic degradation mechanism derived from degradation of pMMA in our previous publication is also relevant to pBA and pHEMA. In addition, pBA and pHEMA are susceptible to other degradation and crosslinking reactions; crosslinking is particularly rapid in pHEMA exposed to UV radiation.
