Chiral BINAP-based hierarchical porous polymers as platforms for efficient heterogeneous asymmetric catalysis

Two vinyl‐functionalized chiral2,2'‐bis(diphenylphosphino)‐1,1'‐binaphthyl(BINAP)ligands,(S)‐4,4'‐divinyl‐BINAP and(S)‐5,5'‐divinyl‐BINAP,were successfully synthesized.Chiral BINAP‐based porous organic polymers(POPs),denoted as4‐BINAP@POPs and5‐BINAP@POPs,were efficiently prepared via the copolymerization of vinyl‐functionalized BINAP with divinyl benzene under solvothermal conditions.Thorough characterization using nuclear magnetic resonance spectroscopy,thermogravimetric analysis,extended X‐ray absorption fine structure analysis,and high‐angle annular dark‐field scanning transmission electron microscopy,we confirmed that chiral BINAP groups were successfully incorporated into the structure of the materials considered to contain hierarchical pores.Ru was introduced as a catalytic species into the POPs using different synthetic routes.Systematic investigation of the resultant chiral Ru/POP catalysts for heterogeneous asymmetric hydrogenation ofβ‐keto esters revealed their excellent chiral inducibility as well as high activity and stability.Our work thereby paves a path towards the use of advanced hierarchical porous polymers as solid chiral platforms for heterogeneous asymmetric catalysis.

Direct conversion of furfural to levulinic acid/ester in dimethoxymethane:Understanding the mechanism for polymerization

This study investigated the conversion of furfural to 5-hydroxymethylfurfural(HMF)and further to levulinic acid/ester in dimethoxymethane under acidic conditions,with the particular focus on understanding the mechanism for polymer formation.The results showed that furfural could react with dimethoxymethane via electrophilic substitution reaction to form HMF or the ether/acetal of HMF,which were further converted to levulinic acid and methyl levulinate.The polymerization of furfural and the cross-polymerization between dimethoxymethane and the levulinic acid/ester produced were the main side reactions leading to the decreased yields of levulinic acid/ester.Comparing to the other solvent,methanol as the co-solvent helped to alleviate but not totally inhibited the occurrences of the polymerization,as the polymerization reactions via aldol condensation did not eliminate the C=O functionalities.As a consequence,the polymerization reactions continued to proceed.Other co-solvent used such as guaiacol,dimethyl sulfoxide and acetone interfered with the transformation of furfural to HMF or aided the polymerization reactions.The polymer produced from the reactions between furfural and DMM was different from that produced from levulinic acid/ester.The former had a higher crystallinity,while the latter was more aliphatic.The DRIFTS and TG-MS studies showed that the polymer had the carboxylic group,methyl group and the aliphatic structure in the skeleton.The removal of these functionalities was accompanied by the aromatization of the polymer.The condensation of DMM with levulinic acid/ester was the key reason for the diminished production of levulinic acid/ester.

Synthesis of optically active polymers bearing amino acid moieties by atom transfer radical polymerization

We report here an approach toward the synthesis of optically active polyacrylamide bearing amino acid moieties, poly[Nmethacryloyl L-leucine methyl ester] （PMALM）, with controlled average number molecular weight （Mn） and relatively narrow polydispersity index （PDI, Mw/Mn 〈 1.3） by atom transfer radical polymerization （ATRP） using initiating system methyl 2-bromopropionate/CuBr/tris（2-dimethylaminoethyl） amine. The optical properties of the resulting polymers were evaluated from specific optical rotation value and CD spectra.

Chemical design and characterization of cellulosic derivatives containing high-nitrogen functional groups:Towards the next generation of energetic biopolymers

In this research,a promising class of insensitive and high-energy dense biopolymers,which contain nitrogen-rich 1H-tetrazol-1-yl acetate and nitrate ester functional groups,was successfully synthesized through tetrazole derivatization and nitration of cellulose and its micro-sized derivative(TNCN and TCMCN).Their molecular structures,physicochemical properties,thermal behaviors,mechanical sensitivities and detonation performances were studied and compared to those of the corresponding nitrocellulose and nitrated micro-sized cellulose(NCN and CMCN).The developed energetic TNCN and TCMCN exhibited insensitive character with excellent features such as density of 1.710 g/cm3and 1.726 g/cm3,nitrogen content of 20.95%and 22.59%,and detonation velocity of 7552 m/s and 7786 m/s,respectively,and thereby demonstrate their potential applications as new generation of energetic biopolymers to substitute the common NCN.Furthermore,thermal results showed that the designed nitrated and chemical modified cellulosic biopolymers displayed good thermal stability with multistep decomposition mechanism.These results enrich future prospects for the design of promising insensitive and high-energy dense cellulose-rich materials and commence a new chapter in this field.

Vinylic polymerization of Norbornenecarboxylic Acid Esters by Palladium Complexes

New thermoplastic norbornene polymers containing ester groups were prepared byvinylic polymerization of norbornene-carboxylic acid esters by Pd(Ⅱ)-based catalysts. Themonomers were obtained by Diels-Alder reaction of cyclopentadiene with acrylic acid esters(methyl and butyl) as mixtures of endo/exo (ratio 40/60)-isomers and were converted topolymers in 60%～70% conversion. The endo-isomer was less reactive than the exo-isomer.To obtain higher molecular weight the more reactive pure exo-isomer was prepared andpolymerized with the Pd (Ⅱ)-catalysts, tetrakis (acetonitrile) Pd (Ⅱ) bis (tetrafluoroborate)and (η3-allyl)Pd(Ⅱ)SbF6, in high conversion. These polymers showed high glass transitiontemperatures, high transparency and good solubility in common solvents.

Utilization of Trimethylolpropane Based Hyperbranched Poly(Amine-Ester) as New Polymeric Admixture

Hyperbranched poly(amine-ester) (HBPAE) was synthesized via pseudo-one-step process between trimethylolpropane as a core molecule and N, N-diethylol-3-amine methylpropionate as the AB2 branched monomer. The prepared polymer was analyzed by IR, GPC, 1H-NMR and thermal analysis (TGA and DSC). The performance of the polymer in cement was tested by measuring the effect of 1, 3 and 5 wt% of HBPAE solutions on the properties of Ordinary Portland Cement. Water of consistency, setting times, bulk density, apparent porosity, compressive strength and combined water content of the polymer/cement pastes were studied. The results showed that water of consistency and apparent porosity decreased while setting times, compressive strength, combined water and bulk density increased with the polymer addition.

Removal of Dye Using Lignin-Based Biochar/Poly(ester amide urethane)Nanocomposites from Contaminated Wastewater

The pursuit of incorporating eco-friendly reinforcing agents in polymer composites has accentuated the exploration of various natural biomass-derived materials.The burgeoning environmental crisis spurred by the discharge of synthetic dyes into wastewater has catalyzed the search for effective and sustainable treatment technologies.Among the various sorbent materials explored,biochar,being renewable,has gained prominence due to its excellent adsorption properties and environmental sustainability.It has also emerged as a focal point for its potential to replace other conventional reinforcing agents,viz.,fumed silica,aluminum oxide,treated clays,etc.This study introduces a novel class of polymer nanocomposites comprising of lignin-based biochar particles and poly(ester amide urethane)matrix via a feasible method.The structural evaluation of these nanocomposites was accomplished using Fourier-transform infrared spectroscopy,X-ray photoelectron spectroscopy,and powder X-ray diffraction.The polymer nanocomposites exhibited superior mechanical properties with an increment in tensile strength factor by 45%in comparison to its pristine matrix,along with an excellent toughness value of 90.22 MJm^(−3)at a low loading amount of only 1 wt%.The composites showed excellent improvement in thermal properties with a sharp rise in the glass transition temperature(Tg)value from−28.15℃to 84℃,while also championing sustainability through inherent biodegradability attributes.Beyond their structural prowess,these polymer nanocomposites demonstrated excellent potential as adsorbents,displaying efficient removal of malachite green and tartrazine dyes from aqueous systems with a removal efficiency of 87.25%and 73.98%,respectively.The kinetics study revealed the pseudo second order model to be the precision tool to assess the dye removal study.Complementing this,the Langmuir adsorption isotherm provided a framework to assess the sorption features of the polymer nanocomposites.Overall,these renewable biochar integrated polymer matrices boast remarkable recovery capabilities up to seven cycles of usage with an excellent dye recovery percentage of 95.21%for the last cycle,thereby defining sustainability as well as economic feasibility.

Study on Polyurethane/(vinyl ester resin) IPN Damping Materials

Polyurethane/(vinyl ester resin) interpenetrating polymer network (PU/VER IPN) materials with broad temperatureranges and excellent damping properties from Iow temperature to room temperature were prepared. The influenceof comonomers and component ratios on the compatibility and damping properties of IPN materials was studied byDMA which indicates that such properties are improved by introducing acrylic esters instead of polystyrene (PSt)into VER comonomer system. The detected results of microstructure by AFM show that the phase ranges of thedual-phase continuous IPN materials obtained are both in nanometer scale. The results of mechanical propertiesshow that IPN materials show the regulation from elastic deformation to brittle deformation with the increase of VERproportion.

SYNTHESIS AND CHARACTERIZATION OF HYPERBRANCHED POLY(ESTER-AMIDE)S BASED ON GALLIC ACID AND DL-2-AMINOBUTYRIC ACID

A novel AB3-type monomer was prepared from gallic acid and DL-2-aminobutyric acid, and used for the synthesis of the biocompatible hyperbranched poly(ester-amide)s by self-polycondensation. The polymers were characterized via FTIR and NMR spectroscopy and thermal analysis, and the average degree of branching of the polymers was estimated to be 0.75. The polymers with abundant acetyl end groups were found to be amorphous with lower intrinsic viscosity, better thermal stability and excellent solubility.

Composition Dependence of the Thermal Behavior,Morphology and Properties of Biodegradable PBS/PTMO Segment Block Copolymer

A series of aliphatic biodegradable poly（ether-ester）s based on poly（butylene succinate）（PBS）as hard segment and poly（tetramethylene oxide）（PTMO,M_n=1 000 g/mol） as soft segment were synthesized.The composition dependence of thermal behavior,morphology and mechanical properties was investigated by differential scanning calorimetry（DSC）,atomic force microscopy（AFM）,and tensile testing.The crystallization temperature（T_c） and melting temperature（T_m） of the PBS block within poly（ether-ester）s decrease steadily at first,but decrease sharply with PTMO content above 50 wt%.Two crystallization peaks were detected for PTMO in PBSPTMO60 sample,suggesting the occurrence of fractionated crystallization.The crystallization enthalpies（△H_c） and melting enthalpies（△H_m） of PBS block decrease at first,then increase as PTMO content increases further.AFM has demonstrated that phase-separated morphology transforms from a phase of continuous hard matrix to one of continuous soft matrix containing isolated hard domain as PTMO content is increased.Finally,the results of tensile testing show that the poly（ether-ester）s present the behavior of plastics when PTMO content is below 40 wt%,and of thermoplastic elastomers with PTMO content above 50 wt%.By varying the composition of copolymer,the aliphatic poly（ether-ester）s plastics,or especially biodegradable aliphatic poly（ether-ester）s thermoplastic elastomers can be obtained.

Synthesis and characterization of new biodegradable thermosensitive polyphosphazenes with lactic acid ester and methoxyethoxyethoxy side groups

Two novel biodegradable thermosensitive polyphosphazenes with lactic acid ester and methoxyethoxyethoxy side groups were synthesized via the macromolecular substitution reactions of poly(dichlorophosphazene) with the sodium salt of lactic acid ester and sodium methoxyethoxyethoxide.Their structures were confirmed by ^(31)p NMR,~1H NMR,^(13)C NMR,IR,DSC,and elemental analysis.The lower critical solution temperature(LCST) behavior in water and in vitro degradation property of the polymers was investigated.The...

Electrochemistry of polyamidoamine dendrimers ester gel electrolytes

This paper described the first example of polyamidoamine dendrimers ester(PAMAM) used as a gel electrolyte with a short-chain polyethylene glycol (MPEG-400) as aplasticizer. The polymer films are solid and sticky. Background cyclic voltammetry (CV) shows apotential window between +0.7 and -0.7 V vs. Ag/AgCl. The voltammetry of ferrocene and7,7,8,8-tetracyanoquinodimethane (TCNQ) indicates that diffusion coefficients are in the range of10^(-8) -10^(-9) cm^2/s. Ionic conductivities are approximately 10^(-6) S/cm. Similar films usingdimethyl sulfoxide (DMSO) as a plasticizer instead of MPEG-400 have demonstrated ionicconductivities of 10^(-4) S/cm and reversible voltammetry. However, UV spectropho-tometry shows that70% of the DMSO is lost under vacuum, indicating the difficulty in quantifying the DMSO contentwhen exposed to vacuum.

In Vitro Antimicrobial Activity Study of Some New Arginine-based Biodegradable Poly （Ester Urethane）s and Poly （Ester Urea）s

Bactericidal activity of some arginine based biodegradable polymers-PEURs （poly （ester urethane）s） and PEUs （poly （ester urea）s） with low cytotoxicity was studied in in vitro experiments. Various bacterial strains both Gram-positive and Gram-negative were used to explore the bactericidal activity of the cationic polymers. As the test objects, the following microorganisms were used： Bacillus subtilis, Staphylococcus aureus, Mycobacterium album, Pseudomonas fluorescens, Escherichia coli, Actinomyces griseus and Aspergillus niger. The obtained results showed that the new cationic polymers suppressed the growth of the studied microorganisms and the bactericidal activity of the tested cationic polymers strongly depending on their chemical structure.

SYNTHESIS AND CHARACTERIZATION OF THERMOTROPIC COPOLYESTERS AND COPOLY (ESTER-AMIDE)S CONTAINING OXYETHYLENE-ETHER AS THE SPACER

Flexible oxyethylene-ether was introduced into the aromatic copolyesters and copoly (ester-amide)s to reduce the melting point of resulting polymers. The melting point was greatly reduced to 200 degrees C or even lower in some cases, and the molecular weight was satisfactorily high as reflected by inherent viscosity. The polymers exhibited high thermal stability and good mechanical properties as determined by TGA and mechanical tests. The copolyester showed better crystallinity and liquid crystallinity than corresponding copoly (ester-amide)s with similar monomer composition as reflected by POM observation and WAXD study. The melting points for both copolyesters and copoly (ester-amide)s showed great dependence on the p-acetoxybenzoic acid (PAB) content in monomer composition and reached the lowest value when PAB was 29 mol%.

Synthesis of Bis(4'-hydroxyphenyl)-toluene-2, 4-diurethane for Main Chain Liquid Crystalline Poly(urethane-ester)s

A new methodology was advanced that mesogenic cores appeared after theformation of urethane groups and during the monomer-to-polymer transition. A newdiphenol monomer, bis(4'-hydroxy-phenyl)-toluene-2 (BHPTU), was obtainedby the reaction of 2,4-tolulene diisocyanate with hydroquinone in dioxane or N,N-dimethyl-acetandde. The reaction process was monitored by FTIR, and the product was investigated bylH NMR and elemental analysis (EA). A liquid crystalline poly(urethane-ester) was obtainedusing the BHPTU monomer.

模糊综合评价模型在高能硝胺发射药改性评价中的应用研究

为研究模糊综合评价模型在高能硝胺发射药改性评价中的应用,采用包覆工艺,分别选取三氨基三硝基苯(TATB)和聚酯(NA)作为包覆工艺中的降燃速材料,制备了TATB包覆发射药和NA包覆发射药,对比了包覆和未包覆发射药的堆积密度、局部燃速、爆热、燃烧渐增性以及内弹道性能;基于此实验结果,采用层次分析法,评价了TATB和NA对发射药基本性质和燃烧性能的影响程度。研究建立了发射药基本性质和发射药燃烧性能间的模糊评价方法;发现面向发射药燃烧性能,局部燃速的影响权重最大,为0.82;爆热的影响权重次之,为0.11;堆积密度的影响权重为0.07。在堆积密度差异较小的情况下,由于NA包覆发射药的降燃速效果明显强于TATB包覆发射药,NA包覆发射药的能量损失虽然较TATB包覆发射药更大,NA包覆发射药的燃烧性能优于TATB包覆发射药,且二者明显强于未包覆的空白发射药。

环糊精超交联聚合物纤维顶空固相微萃取-气相色谱-质谱法分析植物油中的邻苯二甲酸酯

邻苯二甲酸酯(PAEs)因具有改善塑料柔软性和柔韧性的特性而被作为增塑剂广泛应用于各种食品包装材料,然而,其对人类健康的重大危害使得建立准确的分析方法显得至关重要。为了解决油性基质样品前处理费时费力的问题,我们开发了一种基于顶空固相微萃取(HS-SPME)结合气相色谱-质谱(GC-MS)检测的分析方法,用于快速检测植物油基质中的12种PAEs。将苄基化环糊精超交联聚合物(BnCD-HCP)涂敷在不锈钢纤维上制备了一种具有较大比表面积、良好稳定性好和较高重复性的固相微萃取探针,并对其结构、形貌进行了表征。将油脂样品以甲醇改性后以该探针顶空萃取PAEs,优化得到如下最佳萃取参数:萃取时间20 min,萃取温度50℃,解吸时间4 min,解吸温度275℃。在优化的分析条件下,12种目标PAEs在线性范围内具有良好的线性关系(相关系数(R^(2))均大于099),检出限和定量限分别为021~374μg/kg和069~1234μg/kg,单针的相对标准偏差(RSD)≤114%,针间RSD≤139%。将此方法应用于大豆油、花生油和葵花油样品中PAEs的检测,加标试验结果表明该方法具有良好的精密度(RSD为117%~1173)和回收率(7249%~12443%)。该研究建立的基于BnCD-HCP的HS-SPME方法不需要溶剂萃取和净化等繁琐操作,具有快速、灵敏、准确、环保等优点,为植物油中PAEs的灵敏筛检提供了新的方法和技术。

GB/T 42790-2023《丙烯酸共聚聚氯乙烯树脂》标准解读

介绍了GB/T 42790—2023《丙烯酸共聚聚氯乙烯树脂》的制定和发布过程,从标准的制定原则、技术指标的确定和检测方法、检验规则等方面详细解读了标准内容,并总结了部分指标的验证试验过程,为相关使用方深入理解和应用该标准提供指导。

超支化聚(胺酯)的分子设计及其制备

以丙烯酸甲酯和二乙醇胺为原料由Michael加成反应制得N ,N 二羟乙基 3 胺基丙酸甲酯单体 ,再用“准一步法”和“发散法”使之与 1 ,1 ,1 三羟甲基丙烷 (核 )反应合成一种新型超支化聚 (胺 酯 ) .以核磁共振和元素分析方法对N ,N 二羟乙基 3 胺基丙酸甲酯单体的分子结构进行了表征 .GPC测定表明合成的超支化聚 (胺 酯 )分子量分布窄 ,具有单分散性 ;粘度小于同分子量的线形分子 ;耐热性能较好 ,失重温度高于2 0 0℃ .

以季戊四醇为“核分子”超支化聚酯-酰胺的合成及表征

以二异丙醇胺(DIPA)与六氢苯酐(HHPA)为原料合成了一种端基带有一个羧基、两个羟基的AB2型单体。用季戊四醇(PETL)作为“核分子”,按一定的摩尔配比与AB2型单体反应,分别得到两种不同的超支化聚酯酰胺(1GHP、2GHP)。并采用红外光谱(IR)、凝胶渗透色谱法(GPC)、粘度法等方法对其结构进行了表征。结果表明1GHP、2GHP的多分散性指数分别为1.47和2.17,呈现很窄的分子量分布。两种分子的粘度与浓度的关系服从Einstein粘度方程,具有紧凑的球形分子结构。