半乳糖二酸催化脱水环合制备2,5-呋喃二甲酸工艺及动力学

2,5-呋喃二甲酸（2,5-FDCA）是生物质基的平台化合物之一,在聚合物领域有广泛的应用前景。针对半乳糖二酸脱水环合制备2,5-FDCA存在的收率低、动力学数据缺乏等问题,在催化剂和溶剂筛选的基础上,开展了半乳糖二酸制备2,5-FDCA的工艺优化,得到了较佳的工艺条件为15%(质量)硫酸催化、环丁砜为溶剂、130℃下反应16 h,此时2,5-FDCA收率为49.1%。测定了不同硫酸浓度和不同温度下半乳糖二酸脱水环合制备2,5-FDCA反应动力学数据,采用一级反应动力学拟合得到了15%(质量)硫酸催化下半乳糖二酸降解反应活化能为54.4 kJ/mol、2,5-FDCA生成活化能为57.8 kJ/mol、其他副反应的活化能为50.7 kJ/mol、2,5-FDCA进一步降解反应的活化能为130.6 kJ/mol。研究工作对己糖二酸路线制备2,5-FDCA工业化进程有一定的推动作用。     

从生物质衍生原料到2,5-呋喃二甲酸产品的合成研究进展

2,5-呋喃二甲酸（2,5-FDCA）作为呋喃的衍生物,是一种具有良好稳定性和高附加值的生物基平台化合 物,在聚酯、聚酰胺、聚氨酯、热固性材料和塑化剂等众多领域都得到了广泛应用,如何绿色高效地制备 2,5-FDCA是近年来的研究重点。本文综述了以5-羟甲基糠醛（HMF）、糠酸、己糖二酸等生物质衍生原料合成 2,5-FDCA的方法及特点。己糖二酸等其他路线产率较低,不利于工业化的发展。HMF路线与之相比具有产率高和副产物少的优势,但由于原料来源与食品行业相冲突且生产成本较高,所以利用不可食用的生物质衍生原料糠酸低成本合成目标产物将成为未来可持续发展的重要研究方向。在此基础上,本文通过对比糠酸各路线的优缺点后发现,CO{}_{\mathrm{3}}^{\mathrm{2}-}促进的糠酸羧基化合成方法无需反应溶剂,催化剂组分简单可再生,这些都有利于低成本合成产品。且由于工艺流程简单,产物选择性和收率高,糠酸羧基化方法将成为绿色大规模生产2,5-FDCA极具潜力的路线。     

Synthesis and characterization of high molecular weight side chain liquid crystalline/photoactive polymers

Various liquid crystalline and photoactive azobenzene monomers were synthesized and attached to copoly(methyl methacrylate‐glycidyl methacrylate) [copoly (MMA‐GMA)] to get high molecular weight side chain liquid crystalline (LC)/photoactive copolymers. Further, spacers are generated in situ and reactive groups are obtained after the modification. All monomers and polymers were thoroughly characterized by FTIR, ¹H and ¹³C NMR, UV‐VIS spectrophotometry, gel permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, and polarized optical microscopy. All side chain LC polymers showed higher thermal stability than that of copoly(MMA‐GMA). Three LC and one azo monomer exhibited characteristic nematic mesophase where as one LC monomer has shown nematic and sanded smectic‐A texture. The rate of trans‐cis isomerization of polymer was lower than that of the monomer and both monomers and polymers showed slow back isomerization. Present approach offers convenient way to synthesize high/desired molecular weight photoactive LC polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

HBr-MgBr2催化己糖二酸脱水环合制备2，5-呋喃二甲酸的研究

2,5-呋喃二甲酸（2,5-FDCA）是生物可降解塑料聚呋喃二甲酸乙二醇酯的聚合单体,未来需求量巨大。针对己糖二酸脱水环合制备2,5-呋喃二甲酸存在的收率低问题,开展了更高选择性催化体系的构建研究,成功筛选到了两个优良的催化体系：HBr-MgBr₂、HBr-LiBr。3%（质量）HBr-6%（质量）MgBr₂催化、120℃下反应2 h,D-葡萄糖二酸单钾盐脱水环合制备2,5-FDCA收率达到84.2%。当反应底物浓度低于5%（质量）以及水含量从3.3%富集到16.5%时,2,5-FDCA的摩尔收率未见明显下降,且都可维持在80%以上。测定了100~130℃温度范围内3%（质量）HBr-6%（质量）MgBr₂催化D-葡萄糖二酸单钾盐脱水环合制备2,5-FDCA动力学数据,采用一级反应动力学拟合得到2,5-FDCA的生成反应活化能为108.9 kJ/mol、副产物生成活化能为136.6 kJ/mol。研究工作对己糖二酸脱水环合制备2,5-FDCA路线的工业化具有积极推动作用。     

Phase-transfer catalysed synthesis of disubstituted poly(phenylene vinylene)

An attempt to synthesize a series of phenyl ring disubstituted poly(o-, m- and p-phenylene vinylene) is reported. In this ‘one-pot’ reaction, a phase-transfer catalyst was used to promote the extraction of strong base deprotonated bischloromethyl aromatic anions from the aqueous to the organic phase to sustain a nucleophilic substitution reaction with the remaining bischloromethyl monomers. The polymers obtained were characterized for their chemical compositions and physical properties by elemental, i.r. and u.v. spectroscopic, and thermal analyses. The o-substituted polymers were found to have low melting temperatures, good solubilities and high molecular weights, but low yields. The m-substituted monomers, however, produced only non-conjugated poly-m-xylylenes. The p-substituted polymers offered the best combination of yield and physical properties. Films cast from soluble poly(2,5-dibutoxy-p-phenylene vinylene) have electrical volume resistivity in the range 300–500 ohm cm when doped with concentrated sulfuric acid.     

Synthesis and characterization of side‐chain liquid‐crystalline polyacrylates containing azobenzene moieties

Syntheses of novel liquid‐crystalline polymers containing azobenzene moieties were performed by a convenient route with an acrylate backbone. The azobenzenes were key intermediates of the monomers, and side‐chain liquid‐crystalline polymers were prepared, that is, poly[α‐{4‐[(4‐acetylphenyl)azo]phenoxy}alkyloxy]acrylates, for which the spacer length was 3 or 11 methylene units. In addition, poly[3‐{4‐[(3,5‐dimethylphenyl)azo]phenoxy}propyloxy]acrylate was prepared with a spacer length of 3 methylene units. The structures of the precursors, monomers, and polymers were characterized with Fourier transform infrared, ¹H‐NMR, and ¹³C‐NMR techniques. The polymers were obtained by conventional free‐radical polymerization with 2,2′‐azobisisobutyronitrile as an initiator. The phase‐transition temperatures of the polymers were studied with differential scanning calorimetry, and the phase structures were evaluated with a polarizing optical microscopy technique. The results showed that two of the monomers and their corresponding polymers exhibited nematic liquid‐crystalline behavior, and one of the monomers and its corresponding polymer showed smectic liquid‐crystalline behavior. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2653–2661, 2002     

Synthesis and characterization of fluorinated poly(azomethine ether)s from new core-fluorinated azomethine-containing monomers

In this work, we describe the design and synthesis of novel core-fluorinated Schiff base monomers and conjugated polymers based on them. The new fully aromatic highly fluorinated poly(azomethine ether)s (PAMEs) were prepared by polycondensation of core-fluorinated azomethine-containing compounds. The structure of the monomers and polymers were confirmed by FTIR, ¹H, ¹³C, and ¹⁹F NMR spectroscopic analysis. The influence of synthesis condition on the properties of PAME compounds was investigated. Application of polarization microscopy with a temperature control thermal stage revealed thermotropic liquid crystalline (LC) behavior in the synthesized materials. Transition temperatures and a range of the existence of the LC phase were studied by a combination of the optical microscopy and DSC analysis. According to the TGA analysis, all the synthesized PAMEs show high thermal stability and thus offer a wide range of thermal processibility (up to 410–477 °C), which makes them prospective materials for many modern applications.     

Crystallization-induced reactions of copolymers: 6. Reorganization of polyesters in the liquid crystal state

A series of random thermotropic poly(4-oxybenzoate-co-ethylene terephthalate), P(OB/ET), and poly(3-chloro-4-oxybenzoate-co-ethylene terephthalate), P(COB/ET), copolymers were prepared and their thermal properties were determined. The crystallization induced reactions (CIR) of some of these copolymers were investigated in the liquid crystal state. The effects of reaction parameters such as reaction time, temperature, type and amount of catalyst, and molecular weight of the initial sample were examined for yields, compositions, properties and sequence distributions of the reorganized products. The initial liquid crystal copolymers formed a mixture of soluble and insoluble products after the CIR process, and the latter are believed to be multiblock, crystalline oxybenzoate copolymers which are infusible above an average oxybenzoate sequence length of approximately four units.     

Synthesis and characterization of ferroelectric side chain liquid crystal polymers bearing banana-shaped chiral mesogens

A series of ferroelectric liquid crystal polymers having banana-shaped side chain mesogens were synthesized through photo-polymerization of epoxide moiety. 2,5-disubstituted-thiophene sub-unit was used in synthesizing the banana-shaped monomers. These liquid crystal compounds were characterized by NMR, differential scanning calorimetry (DSC) and optical polarized microscopy (POM). Mesomorphism was investigated as a function of spacer units. All the synthesized low molar mass banana-shaped compounds exhibit smectic blue phase, but chiral smectic C phase could be observed only on compounds having longer spacer. The clearing temperature of low molar mass compounds fluctuated a little when spacer length varies. All polymers exhibit cholesteric mesophase and an observable glass transition. These liquid crystalline compounds reveal strong photoluminescence at visible region (λ_max = 475 nm for M9EPX) and have potential use in polarized organic light emitting diode materials.     

Synthesis and Electroluminescence of Side-chain Liquid Crystalline Polyacrylates and Polyoxiranes Containing Bistolane Side Groups

The synthesis and characterization of side-chain liquid crystalline (LC) polyacrylates and polyoxiranes containing bistolane side-groups are presented. The phase behavior of the prepared monomers and polymers was characterized by differential scanning calorimetry and optical polarizing microscopy. All of the obtained monomers and polymers reveal an enantiotropic nematic phase. The birefringences of the LC monomers are in the range from 0.35–0.6 depending on the measuring wavelength. The photoluminescence (PL) and electroluminescence (EL) properties of the obtained monomers and polymers are also reported.     

Synthetic preparations and physical and electrical properties of main chain type thermotropic liquid crystalline polyimide/SiO2 nanocomposites

Two kinds of monomers, 1,3‐bis[4‐(4′‐amino‐Phenoxy)cumyl]benzene (BACB) and pyromellitic dianhydride were used to synthesize the Liquid Crystalline Polyamic acid—a precursor (LCPAA) of Liquid Crystalline Polyimide (LCPi). The nanohybrid films were successfully prepared by the sol–gel reaction. Tetraethoxysilane (TEOS) (99%)–ethanol (99.8%) solution was added to LCPAA solution. The hybrid films were made by the hydrolysis–polycondensation of TEOS–ethanol in the LCPAA solution. When water and the solvent were removed completely, the hybrid films were obtained. The functional group and chemical structure were characterized by FTIR. We employed a number of instruments to understand whether the nano‐SiO₂ particle was introduced into the polymer matrix and enhanced the thermal properties and mechanical strength. The liquid crystalline phase of the LCPi and LCPi/SiO₂ hybrid films was observed by POM. TGA and DSC were used to test the thermal properties. The crystallization and liquid crystal phase analyses were carried out by XRD. The elemental analysis was employed to measure the 1,3‐bis[4‐(4′‐nitrophenoxy)cumyl)]benzene and BACB monomers. Besides, the cross section at morphology of the materials was observed with an FESEM. The electrical properties of hybrid films were measured by the high resistance analysis and dielectric constant analysis. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1688–1704, 2006     

Thermotropic liquid crystalline poly (hydrazone–ether)s containing thiadiazole moiety in the main chain

A new homologous series of thermotropic liquid crystalline poly(hydrazone–ether)s based on the 1,3,4‐thiadiazole moiety in the main chain was synthesized by solution polycondensation of various diformyl‐α,ω‐diphenoxyalkanes with 2,5‐bis(mercaptoacetic hydrazide)‐1,3,4‐thiadiazole. The inherent viscosity of the polymers was prepared in the range of 0.39–0.76 dl g^?1. The phase behaviour of these polymers was studied by differential scanning calorimetry, optical polarizing microscopy using a heated stage, and thermogravimetric analysis. Almost all the polymers exhibited thermotropic liquid crystalline properties. In most cases, the mesophase extends to 335 °C, where thermal decomposition prevents further observation. Methoxy substituents on the benzene ring of these polymers lower the transition temperature significantly. Copyright © 2004 Society of Chemical Industry     

Synthesis and characterisation of a nematic homo-polyurethane

The presence of hydrogen bonds in the chemical structure of polymers promotes and stabilises the crystalline phase. For liquid crystalline (LC) polymers, the side insertion of aliphatic units to the mesogenic unit is a suitable artifice to decrease the crystalline stability, without significantly affecting the stability of the LC phases. Here, we report on the synthesis of a LC homo-polyurethane with high hydrogen bond concentration along the chain and bearing an n-pentyl side-chain. Rheological behaviour, thermal analysis, and X-ray diffraction show that the stable LC phase is the nematic.     

Hydrogen-bond induced side-chain liquid crystalline polymers based on nicotinic acid derivatives

Supramolecular side-chain liquid crystalline poly(acrylate)s have been prepared by self-assembly of H-bond donor and acceptor complexes through intermolecular complementary hydrogen bond formation. Poly[4-(m-acryloyloxyalkyloxy)benzoic acid]s [m = 6 (P1) and 8 (P2)] were employed as polymer components. Liquid crystalline nicotinic acid derivatives (C1, C2, C3, and C4) were used as complementary H-bond donor/acceptor counterparts. The liquid crystalline properties of the nicotinic acid derivatives, the polymers and their complexes were investigated by DSC and POM. Methylene spacers present at the terminal position of the nicotinic acid derivatives played a key role in mesophase arrangements. The columnar phase exhibited by the nicotinic acid derivatives completely disappeared in the H-bonded complexes to afford a nematic phase, thereby substantiating the complex formation.     

液晶热性能的研究

讨论了液晶聚合物及相应的液晶单体的热性能,指出液晶聚合物的液晶温度区间总量宽于液晶单体。通常在侧链液晶聚合物中第二种单体的引 导致液晶温度区间变宽。     

Polydiacetylenes Produced from the Liquid Crystal State

Abstract

The preparation and characterization by standard methods of eleven diphenyldiacetylenes is discussed. All of these materials are liquid crystalline with phase transitions ranging from 90°C to 205°C. The liquid crystal behavior is studied using differential scanning calorimetry and polarized light microscopy. All the materials undergo irreversible polymerization from a liquid crystal state, possibly nematic. at over 210°C. The polymers are red and glassy. Some monomers give promising nonlinear optical results, the polymers are currently being tested. Both monomers and polymers are currently being tested in guest-host systems.     

Synergistic Effects of Polybenzimidazole and Aramide on Enhancing Flame-Retardancy and Solubility

Aromatic and functional polymers with processibility derived from biobased starting materials are prerequisite considering sustainable society. Poly(2,5-benzimidazole)s are rigid-rod polymers to show ultrahigh thermal stability such as flame retardance, while usually suffer from poor solubility. Here, poly(benzimidazole-co-amide)s are synthesized from two biobased monomers, 3,4-diaminobenzoic acid and a semirigid comonomer, 4-aminohydrocinnamic acid. The copolymers with an amide composition of 80 mol% and higher are soluble in widely used polar solvents to fabricate the films keeping high flame retardance, which is comparable with popular high-performance polymers such as aromatic polyimides, polyetheretherketone, polyphenylene sulfide, etc.     

Reduction of dissolved oxygen in boiler water using new redox polymers

New polymers were used as catalysts for the removal of dissolved oxygen in boiler water. These polymers, based upon hydroquinone‐quinone redox system, were prepared by polymerization of methyl 4‐(2,5‐dimethoxybenzyl)cinnamate and copolymerization of this monomer with 4‐(4′‐vinylphenethyl)‐1,10‐phenanthroline. The resulting product was used to synthesize polymers containing transition metal ions. Nuclear magnetic resonance, infrared spectroscopy, and elemental analysis were achieved to characterize monomers and/or electron‐transfer polymers. These polymers were used for the removal of oxygen from water. It was shown that the oxygen content was reduced to less than 0.1 mg L^?1 in ～ 70 s. Based on the obtained results, the redox capacity of two polymers were determined. It was established that the poly‐4‐(2,5‐dihydroxybenzyl)cinnamic acid reached a redox capacity of 69.7 mg of O₂ per gram of polymer. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Thermally induced phase separation in poly(lactic acid)/dialkyl phthalate systems

Thermally induced phase separation in poly(lactic acid)/dialkyl phthalate systems was investigated. Poly(DL ‐lactic acid) (PDLLA) and poly(L ‐lactic acid) (PLLA) with different molecular weights were used. A series of dialkyl phthalates, with different numbers of carbon atoms in the alkyl chain, were employed as solvents to control the interaction between polymer and solvent. The liquid–liquid phase‐separation temperature of the poly(lactic acid) solutions decreased systematically with a shorter alkyl chain in the phthalate. Based on the interaction between polymer and solvent and the molecular weight of polymer influencing liquid–liquid phase‐separation temperature significantly but crystallization temperature only slightly, proper thermal conditions were employed to investigate competitive phase separation and crystallization in PLLA solutions. Factors that can influence the final morphology of PLLA solutions were examined. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2224–2232, 2003     

Dimeric liquid crystalline thermosets from azo-containing diglycidyl ether cured by anhydride

A series of dimeric liquid crystalline (LC) epoxy monomers containing azobenzene group with central spacers of different lengths were synthesized and structurally characterized by ¹H NMR, ¹³C NMR, and elemental analysis. The mesogenic behavior of these monomers was measured by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and X-ray diffraction (XRD). Like other dimeric LC epoxy monomers, the melting points, clear points, and mesophase of these compounds are influenced by the carbon numbers of central spacers. Anhydride was employed to cure the monomers and LCTs with nematic phase were obtained. Thermal properties, dynamic mechanical properties and UV–Vis spectra of the LCTs were studied. The decomposition of the LCTs occurred near 220 °C and followed three stages. The LCTs also had the natural absorbance bonds of azo compounds.