ARCHITECTURE OF LADDER,TUBULAR AND SIEVE-PLATE POLYMERS PREPARED BY STEPWISE COUPLING POLYMERIZATION

'Stepwise-coupling polymerization' (SCP) is a very useful approach for preparing microstructure-controllable ordered network polymers, including soluble one-dimensional ladderlike polymers (LP) and tubular polymers (TP), and two-dimensional sieve-plate polymers. The novel reactive LPs are important precursors of micro-structure controllable polymers such as 'fishbone-' or 'rowboat-' like mesomorphic polymers and their metal complexes as well as tubular polymers (TPs). They are full of great potential for use as advanced materials.

Emitting stability of poly(9,9-dialkylfluorene-co-N-butylcarbazole) by solid-state oxidative coupling polymerization

Dihexylfluorene and N-butylcarbazole were copolymerized by solid-state oxidative coupling polymerization in the presence of anhydrous FeCl3 at room temperature. The solid-state films of the copolymers emitted blue light after beating at 150 ℃ in air for 24 h, no red-shifted emission was observed by fluorescence spectroscopy.

Green Light-Emitting Region-Regular Poly(9,9-Dihexylfluorene-co-Fluorenone) Prepared from Solvent-Free Oxidative Coupling Polymerization

Soluble green light-emitting poly（9,9-dihexylfluorene- co-fluorenone） was synthesized by solvent-free oxidative coupling polymerization of 9,9-dihexylfluorene in a facile one-step reaction. The polymers were characterized by FT-IR, ^1H NMR, ^13C NMR, UV-Vis and fluorescence spectroscopy. The region-regular structure of the polymer linking at 2, 7＇-position on the fluorene moieties was obtained. The FT-IR spectra of the polymers showed fluorenone vibration. The fluorescence spectra of the solid thin film of the polymers displayed green light-emitting, which was emitted from fluorenone moieties produced in the polymerization process.

Oxidative coupling polymerization of p-alkoxyphenols with Mn(acac)2-ethylenediamine catalysts

The oxidative coupling polymerization of p alkoxyphenols with Mn(acac)2ethylenediamine catalysts was carried out. The polymerization of pmethoxyphenol with the manganese(II) acetylacetonate [Mn(acac)2]N,N’diethylethylene diamine catalyst in CH2Cl2 at room temperature under an O2 atmosphere afforded a polymer, which mainly consists of the mphenylene unit, whereas the polymer obtained with Mn(acac)2 was rich in the oxyphenylene structure. The polymer yield and regioselectivity were significantly affected by the monomer and catalyst structures. The former catalyst system was also used for the coupling reaction of 2methoxy 4methylphenol. The corresponding carboncar bon coupling product was isolated with a regioselectivity of 95%.

A Pd-metalated porous organic polymer as a highly efficient heterogeneous catalyst for C–C couplings

An efficient catalyst system based on a Pd-metalated porous organic polymer bearing phenanthroline ligands was designed and synthesized.This catalyst was applied to various C–C bond-forming reactions,including the Suzuki,Heck and Sonogashira couplings,and afforded the corresponding products while exhibiting excellent activities and selectivities.More importantly,this catalyst can be readily recycled.These features show that such catalysts have significant potential applications in the future.

The Copolymers of N-alkyl Carbazole and Stilbene Prepared by Oxidative-coupling reaction

A kind of novel electroluminescence polymer has been prepared by oxidative-coupling polymerization of N-alkyl carbazole and trans-stilbene. The structure of the copolymers was characterized by elemental analysis, UV-vis and FTIR spectra. The copolymers have good solubility in chloroform and acetone. Fluorescence spectra showed that these polymers are blue-light emitting materials.

Surface Modification of Nanometer TiO_2 and Effect of Preparing TiO_2/P(St-co-DVB) Composites by Dispersion Polymerization

Surface modification of nanometer titanium dioxide particles and effect of preparing TiO2/P （St-co-DVB） composites by dispersion polymerization are described. To introduce vinyl group onto the surface of titanium dioxide particles, the titanium dioxide particles were surface-modified with a silicane coupling agent, methacryloylpropyltrimethoxysilicane. Polymer encapsulation in the presence of either modified-titanium dioxide particles or unmodified-titanium dioxide particles was carried out by dispersion polymerization of styrene, divinylbenzene in ethanol medium with polyvinylpyrroliclone as stabilizer, and 2, 2＇-azobis（isobutyronitrile） as initiator. The modified-titanium dioxide was analyzed with Fourier-transform infrared spectroscopy（FTIR）, UV-Vis spectrophotometer, thermo-gravimetric analysis and transmission microscope. The polymer encapsulation of modified-titanium dioxide and unmodified-titanium dioxide particles was confirmed with FTIR and transmission electron microscope. Results show that compared with unmodified-titanium dioxide, modified-titanium dioxide is more suitable for preparing inorganic core/orclanic shell composites.

Surface Modification of Nanometre Silicon Carbide Powder with Polystyrene by Inductively Coupled Plasma

An investigation was made into polystyrene （PS） grafted onto nanometre silicon carbide （SIC） particles. In our experiment, the grafting polymerization reaction was induced by a radio frequency （RF） inductively coupled plasma （ICP） treatment of the nanometre powder. FTIR （Fourier transform infrared spectrum） and XPS （X-ray photoelectron spectroscopy） results reveal that PS is grafted onto the surface of silicon carbide powder. An analysis is presented on the effectiveness of this approach as a function of plasma operating variables including the plasma treating power, treating time, and grafting reaction temperature and time.

Synthesis of Star-like Polybutadienes by a Combination of Living Anionic Polymerization and “Click” Coupling Method

Three-arm and four-arm star-like polybutadienes （PBds） were synthesized via the combination of living anionic polymerization and the click coupling method. Kinetic study showed that the click reaction between the azido group terminated PBd-t-N3 and the alkyne-containing multifunctional linking reagent was fast and highly efficient. All coupling reactions were fully accomplished within 40 min at 50 ℃ in toluene in the presence of the reducing agent Cu（0）, proven by 1H-NMR, FTIR and GPC measurements. For the coupling reactions between the PBd-t-N3 polymer and dialkyne-containing compound, the final conversion of the coupled PBd-PBd polymer was ca. 97.0%. When a PBd-t-N3 polymer was reacted with trialkyne-containing or tetraalkyne-containing compound, the conversion of three-arm or four-arm PBd was around 95.5% or 87.0%, respectively. Several factors influencing the coupling efficiency were studied, including the molecular weight of the initial PBd-t-N3, arm numbers and the molar ratio of the azido group to the alkynyl group. The results indicated that the conversion of the target products would be promoted when the molecular weight of the PBd-t-N3 was low and the molar ratio of the azido to alkynyl groups was close to 1.

Modeling size-dependent thermo-mechanical behaviors of shape memory polymer Bernoulli-Euler microbeam

The objective of this paper is to model the size-dependent thermo-mechanical behaviors of a shape memory polymer (SMP) microbeam.Size-dependent constitutive equations,which can capture the size effect of the SMP,are proposed based on the modified couple stress theory (MCST).The deformation energy expression of the SMP microbeam is obtained by employing the proposed size-dependent constitutive equation and Bernoulli-Euler beam theory.An SMP microbeam model,which includes the formulations of deflection,strain,curvature,stress and couple stress,is developed by using the principle of minimum potential energy and the separation of variables together.The sizedependent thermo-mechanical and shape memory behaviors of the SMP microbeam and the influence of the Poisson ratio are numerically investigated according to the developed SMP microbeam model.Results show that the size effects of the SMP microbeam are significant when the dimensionless height is small enough.However,they are too slight to be necessarily considered when the dimensionless height is large enough.The bending flexibility and stress level of the SMP microbeam rise with the increasing dimensionless height,while the couple stress level declines with the increasing dimensionless height.The larger the dimensionless height is,the more obvious the viscous property and shape memory effect of the SMP microbeam are.The Poisson ratio has obvious influence on the size-dependent behaviors of the SMP microbeam.The paper provides a theoretical basis and a quantitatively analyzing tool for the design and analysis of SMP micro-structures in the field of biological medicine,microelectronic devices and micro-electro-mechanical system (MEMS) self-assembling.

Self-consistent Field Crystal Orbital Study on One-dimensional C_(60)Polymer

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POLYMER-SUPPORTED GRIGNARD REAGENT AND ITS USE IN THE FUNCTIONALIZATION OF POLYMER

Polymeric Grignard Reagent (PGR) based on the chloromethylated poly(ST-co-DVB) resinhas been prepared by means of anthracene-magnesium complex in THF (Anth-Mg-THF), andpolymer matrix with long polymethylene spacer was synthesized via the coupling reaction betweenPGR and α, ω-dibromoalkanes. Based on the studies of factors affecting the coupling, such ascatalyst,reaction time,the length of spacer etc.,this paper offers the optimal reaction conditionsand three typical experiment procedures. The mechanism for the formation and coupling reactionof PGR are also discussed.

CATase-immobilized hydrogel platform molded by photo-enzyme coupling polymerization for effectively preventing postoperative abdominal adhesion

Redox homeostasis,which is regulated by enzymes acting as regulatory valves,is crucial for maintaining the proper functioning of biomolecules and a stable microenvironment for physiological processes by modulating the homeostasis of reactive oxygen species(ROS).Antioxidant enzymes in biocatalysis are used in the prevention or treatment of oxidative stress-related disease by counteracting the harmful effects of ROS.However,designing a system that can efficiently immobilize antioxidant enzymes with high catalytic activity and stability is still challenging.Bioinspired by photo-biocatalysis,a novel and effective catalase(CATase)-immobilized hydrogel platform has been developed by the proposed photo-enzymatic coupled radical polymerization strategy of the visible light coupling with the porphyrin-centered CATase.The higher catalytic stability and activity can therefore be achieved due to the preferential polymerization of CATase-immobilized hydrogel platform with a favorable three-dimensional network of enhanced coupling efficacy between light and enzymes.The mechanisms of free radical-initiated polymerization as well as the antioxidant cycle in the photo-CATase coupling system have been explored.Intriguingly,the CATase-immobilized hydrogel platform affords an unprecedented antioxidant ability to scavenge ROS and provide an effective cellular protection mechanism against external oxidative stress.Additionally,the CATase-immobilized hydrogel platform can effectively prevent peritoneal adhesion by reducing the expression of inflammatory cytokines.Therefore,the novel CATase-immobilized hydrogel platform is a potential candidate for physical barriers that effectively prevent postoperative adhesion formation,offering a new anti-adhesion strategy for clinical applications.

Photorefractive Effect in a CdS Nanoparticlessensitized Polymer Composite

The photorefractive （PR） performance of an organic/inorganic hybrid polymer composite sensitized by CdS nanoparticles, combining poly（N-vinylcarbazole） （PVK）, the second-order optically nonlinear chromophore 1-n-butoxy-2-methyl-（4-p-nitropheylazo）benzene （BMNPAB） and 9-ethylcarbazole （ECZ） was studied. It was confirmed that the CdS colloidal particles had a nanoscale size and quantum confinement effect adopting transmission electron microscopy and UV-Vis absorption spectroscopy. The addition of CdS nanoparticles as a photosensitizer in PVK will be significant enhancement of photoconductivity because of the high photocharge generation quantum efficiency and high charge transport to conducting polymer. The polymer composite film exhibited PR effect with a method of two-beam coupling experiment. And an asymmetric two. beam coupling gain of 45.8 cm^-1 without applied electric filed is obtained at 632.8 nm wavelength.

Ultrathin organic polymer with p-πconjugated structure for simultaneous photocatalytic disulfide bond generation and CO_(2)reduction

Combining photocatalytic organic reactions with CO_(2)reduction is an efficient solar energy utilization mode,but it is still limited by the organic species that can be matched and the low conversion.Herein,ultrathin organic polymer with p-πconjugated structure(TPP)was rationally designed and prepared,and showed a high yield of CO(15.2 mmol g^(-1))and conversion of SAS coupled products(100%),far exceeding the organic polymer with P=O structure.The enhanced photoredox activity of TPP is ascribed to the orbital interaction between the p-orbital on phosphorus and theπ-orbitals of aromatic,which can accelerate the photoinduced charge carrier separation and improve the CO_(2)adsorption capacity.TPP can also be used for the dehydrocoupling of various benzyl mercaptans to the corresponding SAS bond products.This work provides a new concept for the efficient synthesis of disulfide bonds combined with CO_(2)reduction in a photoreaction system.

原位聚合法制备连续玻璃纤维增强尼龙6复合材料的改性和性能

尼龙6(PA6)树脂具有优异的性能,其连续纤维复合材料在汽车、航空航天领域具有广泛应用。但是PA6树脂熔融后黏度较高,不易对连续纤维充分浸渍,并且连续纤维与PA6的复合材料界面黏附性较差,限制了其复合材料的性能和应用。针对这些问题,文中对连续玻璃纤维增强尼龙6(CGF/PA6)复合材料开展了研究。首先,采用阴离子开环聚合制备PA6,确定了其最佳制备工艺;其次,用硅烷偶联剂KH550(AP)对连续玻璃纤维(CGF)进行改性,并对其进行了红外光谱表征;最后,通过原位聚合法制备了CGF/PA6复合材料,研究了AP改性对CGF/PA6复合材料力学性能的影响,并对CGF/PA6复合材料的拉伸断口进行了扫描电镜分析。结果表明,AP被键合到了CGF表面,AP改性可以增强CGF/PA6复合材料的界面黏附性,从而使CGF/PA6复合材料的拉伸强度得到改善,当AP用量为2%时,CGF/PA6复合材料的拉伸强度高达88.52 MPa,此时,复合材料的断裂伸长率最低,为4.90%。CGF/PA6复合材料的冲击强度变化不大,均在50 k J/m2左右,说明复合材料的韧性受CGF表面改性影响较小。

星形多臂丁苯共聚物的分子结构设计与合成

以正丁基锂为引发剂、苯乙烯与丁二烯为单体、双四氢糠丙烷为极性结构调节剂、六氯乙硅烷为偶联剂,采用活性负离子聚合技术设计并合成了一系列具有星形结构的多臂丁苯共聚物(S-g-SSB-6)。使用凝胶渗透色谱分析了S-g-SSB-6的分子量及其分布、偶联臂数和偶联效率,使用旋转流变仪测试了S-g-SSB-6、以SiCl_(4)为偶联剂的星形多臂丁苯共聚物及线型结构丁苯共聚物(L-SSB)的流变性能,并考察了支链长度和支链柔顺性对S-g-SSB-6流变性能的影响。结果表明,S-g-SSB-6的偶联臂数达到4.1、偶联效率均大于80%;相同重均分子量下S-g-SSB-6的熔体黏度较L-SSB更低、流体流动性更好;当支化度相同时,S-g-SSB-6的熔体黏度随着单臂分子量和分子链刚性的增加而增大。

Semi-heterogeneous photo-Cu-dual-catalytic cross-coupling reactions using polymeric carbon nitrides

A merger of copper catalysis and semiconductor photocatalysis using polymeric carbon nitride(PCN)for multi-type cross-coupling reactions was developed.This dual-catalytic system enables mild C-H arylation,chalcogenation,and C-N cross-coupling reactions under visible light irradiation with a broad substrate scope.Good-to-excellent yields were obtained with appreciable site selectivity and functional group tolerance.Metal-free and low-cost PCN photocatalyst can easily be recovered and reused several times.

京津冀城市群城镇化与生态环境耦合协调机理及影响因素研究

为探究生态环境保护与城市群城镇化协同发展,以京津冀城市群为研究区域,通过熵权法、耦合协调模型和逐步回归模型,测度了2012—2021年京津冀城市群城镇化与生态环境系统的耦合协调度,对城市群及内部各发展阶段城市的耦合协调发展主控要素进行识别。结果显示:京津冀城市群城镇化与生态环境耦合协调性逐渐增强;城市群城镇化与生态环境耦合协调空间演化呈现为“中心协调,外围失调”的环状分布格局,两极分化严重但差距在逐步缩小;城市群耦合协调发展水平受人口城镇化、经济城镇化、水资源和生态资源影响最大,协调发展型城市和过度发展型城市主要受创新能力、政策要素和生态资源的影响,失调发展型城市受到人才资源、创新能力影响较大。在此基础上,提出发挥中心城市辐射带动优势、关注影响因素作用和制定针对性区域发展规划的对策建议。