Synthesis of Highly Regioregular,Head-to-Tail Coupled Poly(3-octylesterthiophene) via C―H/C―H Coupling Polycondensation

Highly regioregular,head-to-tail coupled poly(3-octylesterthiophene)was synthesized by the Pd-catalysed oxidative the effects of various reaction factors including polymerization temperature,solvents and catalysts etc.on the yield,molecular weight and structural regioregularity of the resultant polymers were systematically studied.The optical,electrochemical and crystallization properties of the resultant P3OET with different HT regioregularities in solution and film state were studied by UV-Vis and fluorescent spectroscopy,cyclic voltammetry and X-ray diffraction(XRD),resepectively.     

Communication: Synthesis of 3-O-Benzyl-β-L-Arabinofuranose 1,2,5-Orthopivalate as a Starting Monomer for Ring-Opening Polymerization

We have studied the ring-opening polymerizations of a variety of glucose orthoester derivatives and found that substituents on the monomer play an important role in stereo- and regioregularity of the resulting polymers.^1-3 These substituent effects open the possibility of application to ring-opening polymerizations of other sugar orthoesters to give stereo- and regioregular polysaccharides. Additionally, the ring-opening polymerization of the galactose orthoester derivative⁴ gave stereoregular (1→5)-β-D-galactofuranan.     

Synthesis of Highly Regioregular,Head-to-Tail Coupled Poly(3-octylesterthiophene) <Emphasis Type="Italic">via</Emphasis> C—H/C—H Coupling Polycondensation

Highly regioregular, head-to-tail coupled poly(3-octylesterthiophene) was synthesized by the Pd-catalysed oxidative C—H/C—H coupling polycondensation. The regioregularity of polymer products was confirmed by the ¹H-NMR technique. Furthermore, the effects of various reaction factors including polymerization temperature, solvents and catalysts etc. on the yield, molecular weight and structural regioregularity of the resultant polymers were systematically studied. The optical, electrochemical and crystallization properties of the resultant P3OET with different HT regioregularities in solution and film state were studied by UV-Vis and fluorescent spectroscopy, cyclic voltammetry and X-ray diffraction (XRD), resepectively.     

Unprecedented Regioregular Poly(1,4‐arylene)s Prepared by Nickel(II)‐Catalyzed Cross‐Coupling Polymerization of 2,5‐Disubstituted Bromo(chloro)arylene

The unprecedented synthesis of regioregular head‐to‐tail‐type poly(1,4‐arylene)s bearing different substituents at the 2‐ and 5‐positions is described. They were prepared by the polymerization of 2,5‐disubstituted bromo(chloro)arylenes by selective halogen–metal exchange with a Grignard reagent and subsequent cross‐coupling polymerization with a nickel catalyst [NiCl₂(dppp)]. Formation of the regioregular poly(1,4‐arylene)s were confirmed by NMR spectroscopy, and showed remarkable differences to those polymers having uncontrolled regioregularity. Polymerization of bromo(chloro)arylenes with a chiral alkoxy substituent also led to the regioregular head‐to‐tail‐type polyarylene, which demonstrated circular dichroism, thus suggesting formation of a structure with higher‐order regularity.     

Study of the order-disorder transitions in methoxy-functionalized polyalkylthiophenes

This article describes the solvatochromic properties of two polyalkylthiophene (PAT) samples functionalized at the end of the hexamethylenic side-chains with a methoxy group, which is able to strongly enhance the solubility, workability and filmability of this kind of polymers. The latter are obtained using either a regioselective or a regiospecific polymerization procedure, thus leading to a different configurational order in the final polymer. The optical features of the synthesized samples—which are very interesting for chemosensor and electrooptical applications—are observed in many solvent/non-solvent systems and derive from the conformational modification of the conjugated backbone induced by side-chain order-disorder transitions. These transitions strongly depend on the content of HT dyads; a fact which undeniably shows the importance of the polymer configuration, directly deriving from the adopted polymerization method, on the final electrical and electronic properties of the obtained material. The low sensitivity of the regioregular sample towards the temperature changes together with its higher tendency to give thick, semicrystalline and self-consisting films makes it very promising for the obtainment of organic semiconductors for electronic devices subjected to high temperature variations.     

手性取代聚(对亚苯基亚乙炔基-alt-间亚苯基亚乙炔基)的设计合成及其手性光性能研究

设计合成了两种主链结构相同、但取代方式不同的带有(-)-trans-桃金娘烷氧基手性侧基的规整连接聚(对亚苯基亚乙炔基-altr-间亚苯基亚乙炔基)(Myr-PMPE-1和Myr-PMPE-2),其中Myr-PMPE-1分子中手性取代基在分子链上均匀分布,而Myr-PMPE-2分子中手性取代基的分布则交替地存在局部"拥挤"和局部"松散".利用紫外-可见吸收光谱、荧光光谱和圆二色谱对两种聚合物膜的手性光性能进行了研究.结果表明,退火处理对Myr-PMPE-1膜的UV吸收和荧光光谱以及光学活性的影响都不明显,其最大不对称因子|gmax|为1.62×10-4;而退火处理对Myr-PMPE-2膜影响显著,未经退火处理或退火温度≤100℃时,Myr-PMPE-2膜几乎不显示光学活性,但当退火温度高于120℃时,随着退火温度的升高和退火时间的延长,Myr-PMPE-2膜的UV吸收和荧光光谱均稍有红移,特别是膜的光学活性显著提高,经140℃退火处理4 h后,其|gmax|可达3.07×10-3,比Myr-PMPE-1膜的高出1个数量级.     

Reactivity of styrene and substituted styrenes in the presence of a homogeneous isospecific titanium catalyst

The isospecific polymerization of several para‐substituted styrenes was performed in the presence of the catalyst dichloro[1,4‐dithiabutanediyl‐2,2′‐bis(4,6‐di‐tert‐butyl‐phenoxy)]titanium activated by methylaluminoxane. All the polymers were highly regioregular and isotactic with narrow molecular weight distributions. The presence of electron‐donating substituents on the aromatic ring had a positive effect on the catalyst activity, whereas electron‐withdrawing substituents affected the polymerization activity negatively. Binary copolymerizations of the various substituted styrenes showed an inversion of the reactivity with respect to that observed in the homopolymerization. These results suggested that the last monomer unit of the polymer chain coordinated to the metal center, influencing the reactivity of the catalyst with respect to the incoming monomer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1486–1491, 2006     

Random copolymers based on 3‐hexylthiophene and benzothiadiazole with induced π‐conjugation length and enhanced open‐circuit voltage property for organic photovoltaics

A series of donor‐acceptor low‐bandgap conjugated polymers, that is, HThmBT (m = 3, 6, 9, 12, 15), composed of regioregular 3‐hexylthiophene segments and 2,1,3‐benzothiadiazole units, were synthesized through the Stille coupling polymerization to optimize the π‐conjugation length of the polymer and the intramolecular charge transfer (ICT) effect in the polymer backbone. The polymers had relatively low optical bandgaps ranging from 1.6 to 1.72 eV. Among these polymers, HTh6BT exhibited the best device performance with a power conversion efficiency (PCE) of 1.6%. Moreover, despite being based on thiophene, HTh6BT exhibited a high‐open circuit voltage (V_OC) of over 0.8 V because of its low high occupied molecular orbital (HOMO) energy level. These results provided an effective strategy for designing and synthesizing low‐bandgap conjugated polymers with broad absorption ranges and well‐balanced energy levels. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Side‐chain ferrocene‐containing (meth)acrylate polymers: Synthesis and properties

A comprehensive investigation on the synthesis and properties of a series of ferrocene‐containing (meth)acrylate monomers and their polymers that differ in the linkers between the ferrocene unit and the backbone was carried out. The side‐chain ferrocene‐containing polymers were prepared via atom transfer radical polymerization. The kinetic studies indicated that polymerization of most monomers followed a “controlled”/living manner. The polymerization rates were affected by the vinyl monomer structures and decreased with an increase of the linker length. Methacrylate polymerization was much faster than acrylate polymerization. The optical absorption of monomers and polymers was affected by the linkers. Thermal properties of these polymers can be tuned by controlling the length of the linker between the ferrocene unit and the backbone. By increasing the length of the linker, the glass transition temperature ranged from over 100 to ?20 °C. Electrochemical properties of both monomers and polymers were characterized. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Inorganic-Organic Hybrid Polymers Based on Surface-Modified Metal Oxide Clusters

Transition metal oxide clusters with unsaturated carboxylate ligands bonded to their surface were polymerized in the presence of organic co-monomers by various polymerization techniques to form cluster-reinforced polymers. The properties of the cluster-crosslinked hybrid polymers are distinctly different to those of the parent polymers and originate from both crosslinking and filler effects. Variation of the cluster proportion, the kind of employed cluster, the ratio of functional and non-functional capping ligands and the polymerization conditions allows modifying the materials properties of the hybrid materials. The most important changes in materials properties compared with the cluster-free polymers relate to the swelling behavior, thermal stability and mechanical properties. Furthermore, cluster-specific properties can be introduced into the polymers, such as magnetic properties.     

Conducting Block Copolymer Nanowires Containing Regioregular Poly(3‐Hexylthiophene) and Polystyrene

Grignard Metathesis polymerization (GRIM) for the synthesis of regioregular poly(3‐alkylthiophenes) proceeds via a “living” chain growth mechanism. Due to the “living” nature of this polymerization regioregular poly(3‐alkylthiophenes) with predetermined molecular weight, narrow molecular weight distributions and desired chain end functionality are now readily available. Allyl terminated poly(3‐hexylthiophene) was successfully used as a precursor for the synthesis of di‐block copolymers containing polystyrene. The addition of “living” poly(styryl)lithium to the allyl terminated regioregular poly(3‐hexylthiophene) generated the di‐block copolymer. Poly(3‐hexylthiophene)‐b‐polystyrene was also synthesized by atom transfer radical polymerization. Integration of poly(3‐hexylthiophene) in di‐block copolymers with polystyrene leads to the formation of nanowire morphology and self‐ordered conducting nanostructured materials.     

Synthesis and characterization of all‐conjugated copolymers of 3‐hexyl‐thiophene and EDOT by grignard metathesis polymerization

Random regioregular copolymers of 3‐hexylthiophene and 3,4‐ethylenedioxythiophene were synthesized by grignard metathesis polymerization. Soluble copolymers were obtained with a high degree of regioregularity and with a monomer ratio close to the feed ratio. A comparison between the optical properties and the thin film morphologies of these copolymers and poly(3‐hexylthiophene) is also presented. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Ultrafast cyclopolymerization for polyene synthesis: living polymerization to dendronized polymers

We discovered that ultrafast cyclopolymerization of 1,6-heptadiyne derivatives reached completion in 1 min using a third-generation Grubbs catalyst. After optimization, this superior catalyst selectively produced conjugated polymers having a five-membered-ring structure with excellent molecular weight control and narrow polydispersity index (PDI). This living polymerization allowed us to prepare fully conjugated diblock copolymers with narrow PDIs. Lastly, this catalyst was active enough to polymerize macromonomers with G-3 dendrons in a living manner as well. This dendronized polymer with a highly regioregular polymer backbone and bulky dendrons was visualized by atomic force microscopy, which revealed the structure of a single molecular wire surrounded by insulating dendrons.     

A direct route to polythiophenes displaying lateral substituents: Easy one‐step synthesis and polymerization of thiophene monomers substituted by a dimethylenecarboxylate (CH2CH2COOR) appendage on the 3‐position

Thiophene monomers displaying a dimethylenecarboxylate (CH₂CH₂COOR) substituent on the 3‐position of the aromatic ring can be easily obtained and in one step from the electrochemically induced reaction of 3‐bromothiophene with the corresponding acrylate (CH₂?CHCOOR). The synthesis of the ethyl ester monomer, of related 2,5‐dihalogenothiophenes, and their polymerization are reported. Despite the surprisingly low solubilities displayed by the polymers, a full spectroscopic characterization could be performed and the data fully analyzed. Oxidative polymerizations (FeCl₃ or electropolymerization) yield a regioirregular polythiophene, with 60–70% of head‐to‐tail diads. Both experimental and theoretical results suggest that the nonconjugated ester plays a very minor role—if any—in the polymerizations under oxidative conditions, but has a significant influence on the polymer properties. Preliminary attempts to polymerize the dihalogenothiophenes under reductive conditions were hampered by the even lower solubilities exhibited by the regioregular oligomers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Systematic Investigation of the Effect of Polymerization Routes on the Gas‐Sorption Properties of Nanoporous Azobenzene Polymers

Functional‐group‐oriented polymerization strategies have contributed significantly to the initial development of porous polymers and have led to the utilization of several well‐known organic transformations in the synthesis of these polymers. Because there are multiple polymerization routes that can be used to introduce the same chemical functionality, it is very important to demonstrate the effect of different polymerization routes on the gas‐sorption properties of these chemically similar polymers. Herein, we have studied the rich chemistry of azobenzenes and synthesized four chemically similar nanoporous azobenzene polymers (NABs) with surface areas of up to 1021 m² g^?1. The polymerization routes have a significant impact on the pore‐size distributions of the NABs, which directly affects the temperature dependence of the CO₂/N₂ selectivity. A pore‐width maximum of 6–8 Å, narrow pore‐size distribution, and small particle size (20–30 nm) were very critical for high CO₂/N₂ selectivity and N₂ phobicity, which is associated with azo linkages and realized at warm temperatures. Our findings collectively suggest that an investigation of different polymerization routes for the same chemical functionalization is critical to understand fully the combined effect of textural properties, local environment, and chemical functionalization on the gas‐sorption properties of nanoporous polymers.     

Polypropylene Modification by the Radiation Graft Polymerization of N-Vinylcaprolactam

The radiation graft polymerization of N-vinylcaprolactam onto polypropylene films was studied. The radiation graft polymerization was performed with preirradiation in air (peroxide method) or using a direct method in aqueous solutions and organic solvents. The effects of radiation dose, reaction time, monomer concentration, and homopolymerization inhibitor on the radiation graft polymerization were studied. It was found that the radiation graft polymerization from a monomer emulsion in water occurred at the highest rate. The IR spectra of grafted polymers were obtained. With the use of differential scanning calorimetry and equilibrium swelling in water, it was found that the modified polymers of polypropylene with grafted poly(N-vinylcaprolactam) chains exhibited thermoresponsive properties.     

Novel synthesis of photocrosslinkable polymers

A new preparative route to photocrosslinkable polymers in which the polymers are produced directly from the polymerization of vinyl monomers having photocrosslinkable groups has been investigated. The photosensitive resins thus produced have higher sensitivity and resolution than conventional photosensitive resins. The monomers were synthesized from the esterification of vinylphenols or vinyl β-chloroethyl ether with cinnamic acid, β-styrylacrylic acid, and their homologs, and from the etherification of vinyl β-chloroethyl ether with hydroxychalcones. Homopolymerizations of these monomers and their copolymerizations with other comonomers were investigated with the use of both radical and ionic initiators. It is shown that radical polymerization of the monomers gave soluble polymers only at low conversion. Anionic initiators did not initiate polymerization. Cationic polymerization imparted soluble polymers in high yield, except for the monomers bearing cyano groups, which generally gave insoluble polymers. Infrared and NMR spectroscopic investigation of the cationically obtained soluble polymers and comparative investigation by cationic polymerization of model compounds indicated that polymerization of the monomers proceeds through the vinyl double bond without affecting the photosensitive unsaturated bond. Thus, linear photocrosslinkable polymers with an intact photoreactive group may be produced by cationic polymerization. In general, these polymers have uniform structure and modifiable physical properties depending on the monomer used. The polymer thus obtained from β-vinyloxyethyl cinnamate has been shown to have excellent properties for use as a photo-resist.     

Emulsion polymerization of acrylonitrile. Part I. Role and effect of emulsifiers in the emulsion polymerization of acrylonitrile

The role in and effects on the emulsion polymerization of acrylonitrile (AN) of three different groups of emulsifiers, i.e., low molecular emulsfiers, well-known water-soluble polymers, and new water-soluble polymers containing a sulfonate group have been investigated by a dilatometry and electron microscopy. The major part of this paper concentrates on the study of the relation between the properties of the third group of emulsifiers and emulsion polymerization characteristics of AN such as rate, degree of polymerization, diameter and number of particles, and the degree of dispersion, by adding copolymers of AN and sodium p-styrenesulfonate (SSS) having various compositions. In the emulsion polymerization of AN, the hydrophobic portion of the emulsifier seems to act as a kind of nucleus around which polymer molecules precipitate and particle formation may occur, and the hydrophilic portion stabilizes the polymer particles thus formed. As the number of particles and the degree of dispersion increases, the total surface of the particles increases, which may raise the overall rate of polymerization due mainly to an increased polymerization on the surface of the polymer particles. The well-known emulsifiers may be classified by the properties and ratio of the nucleus portion and the stabilizing portion. The unusual effect of emulsifiers on the degree of polymerization may be explained by a chain-transfer mechanism.     

An Ultrahigh Mobility in Isomorphic Fluorobenzo[c][1,2,5]thiadiazole‐Based Polymers

To understand the effects rendered on the relevant basic physical properties and device function by controlling the regiochemistry of the cyclopenta[1,2‐b:5,4‐b′]dithiophene‐fluorobenzo[c][1,2,5]thiadiazole polymer (hereafter referred to as the CDT‐FBT polymer), two polymers, the regiorandom polymer (RA) and regioregular version (RR), respectively, are synthesized and characterized. In addition, an efficient route for synthesizing a key monomer for RR using various synthesis scope and optimizing the reaction conditions is discussed. Although RA exhibits optical, electrochemical, and morphological properties similar to RR, it shows better field‐effect transistor (FET) performance. Surprisingly, by employing a capillarity‐mediated sandwich‐casting process on a nanogrooved substrate, an unprecedented mobility of 17.8 cm² V^?1 s^?1 is obtained for RA‐based FETs; this mobility value is almost twofold greater than those of the corresponding RR‐based FETs. For the first time, this study challenges previously reported results in that high carrier mobility is related to the high degree of polymer order induced by the backbone regioregularity.     

丙烯酰胺类聚合物合成方法研究进展

丙烯酰胺类聚合物具有优异的增稠、絮凝、吸湿特性,是水溶性聚合物中重要的品种之一.本文从水溶液聚合、分散聚合、反相悬浮聚合、反相微乳液聚合、胶束共聚合、双水相聚合、模板聚合、超临界CO2中聚合、离子液体中聚合和活性/可控自由基聚合等方面对丙烯酰胺类聚合物的合成方法研究作了全面的总结,同时简要评述了各种合成方法的特点,认为反相微乳液聚合、离子液体中聚合及活性/可控自由基聚合等方法具备独特的优势,并对丙烯酰胺类聚合物今后的发展前景作出了预测.