Synthesis of polyamides from substituted fluorene and diamides in the presence of a copper(I) catalyst

2,7‐Dibromo‐9,9‐dioctylfluorene was synthesized by a two‐step reaction from fluorene and n‐octylboromide. This was reacted with benzamide for the preparation of a model compound and with terephthalamide, isophthalamide, and adipamide for the preparation of polyamides in the presence of a mixture of 10 mol % CuI and 20 mol % N,N′‐dimethylethylenediamine as a catalyst and K₂CO₃ as a base. The monomer and the model compound were characterized with Fourier transform infrared, proton nuclear magnetic resonance, and elemental analysis. The prepared polyamides were characterized with Fourier transform infrared, proton nuclear magnetic resonance, differential scanning calorimetry, thermogravimetric analysis, and solubility and viscosity measurements. The obtained polyamides possessed excellent solubility in common organic solvents, and they exhibited inherent viscosities in the range of 0.93–1.19 dL/g. According to the differential scanning calorimetry analysis, the glass‐transition temperatures of the polyamides were in the range of 84–154°C. Thermogravimetric analysis indicated that a 2% weight loss of the polyamides occurred in the temperature range of 218–253°C under a nitrogen atmosphere. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

聚丙烯催化剂内给电子体9,9-双(苯甲酸甲酯基)芴的合成与表征

以自制的9,9-双羟甲基芴(BHMF)和苯甲酰氯为原料,以三乙胺为吸收剂合成了9,9-双(苯甲酸甲酯基)芴,采用了红外光谱和核磁共振氢谱等分析测试手段对产品进行了结构表征并逐一归属。考察了原料配比、反应时间、反应温度及吸收剂用量等因素对9,9-双(苯甲酸甲酯基)芴收率的影响。实验结果表明,最佳工艺条件为:0.1 mol BHMF,n(BHMF)∶n(苯甲酰氯)=1.0∶3.0,三乙胺吸收剂为60 mL,反应温度10℃,反应时间4.0 h,在此条件下9,9-双(苯甲酸甲酯基)芴收率可达85.4%。     

Synthesis and characterization of new polyamides derived from 1,3-bis[4-(4-aminophenoxy)phenyl]adamantane

Several new polyamides were synthesized by direct polycondensation of the 1,3-bis[4-(4-aminophenoxy)phenyl]adamantane ( I ) with various dicarboxylic acids. The polyamides had inherent viscosities and number-average molecular weights (M_n) of 0.46–0.96 dL/g and 28,000–109,000, respectively. All polyamides III had good solubilities and were soluble in N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), and pyridine. Polyamides had tensile strengths of up to 72.3 MPa, elongation to breakage values of up to 10.2%, and initial modulus of up to 2.1 GPa. Their glass transition temperatures were found to be 228–269°C and 252–307°C using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA), respectively. The melting temperature of III_f was observed at 318°C using DSC. The temperatures of polyamides III at a 5% weight loss ranged from 395 to 435°C in air and from 400 to 450°C in a N₂ atmosphere. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:315–321, 1998     

Synthesis and characterization of polymers derived from selenophene

The synthesis of poly(2,5‐selenophen‐oxo‐1,4‐phenylen‐selenide‐1,4‐phenylene‐oxo) (I) and poly(2,5‐selenophen‐oxo‐1,4‐phenylen‐diselenide‐1,4‐phenylen‐oxo) (II) by reaction of 2,5‐bis(1,4‐bromo‐phenylen‐oxo‐)‐selenophene with sodium selenide or diselenide, respectively, using dimethylformamide as solvent, is described. Both monomers and polymers were characterized by elemental analysis, melting point, and FTIR spectroscopy. Polymers I and II were doped with iodine and SbF₅ and characterized by SEM and XPS. Also, the conductivity and the T_g values were determined. For both polymers the best doping agent was iodine, although polymer II always presented higher conductivity, reaching values of about 6 · 10^?9 S · cm^?1. The T_g values suggest a likely crosslinking of the chains in polymer II when doped with SbF₅. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2019–2026, 2001     

Synthesis and characterization of novel Schiff‐base polyamides from copper/benzil bisthiosemicarbazone complexes

A new copper‐containing Schiff‐base diamine, benzil bis(thiosemicarbazonato)copper(II) (CuLH₄), was synthesized in two steps from benzil bisthiosemicarbazone (LH₆). The ligand LH₆ and the complex CuLH₄ were characterized with Fourier transform infrared spectroscopy, ¹H‐NMR, and elemental analysis. CuLH₄ was used to prepare novel polyamides. The low‐temperature solution polycondensation of the complex CuLH₄ with various aromatic and aliphatic diacid chlorides afforded copper‐containing Schiff‐base polyamides with inherent viscosities of 0.25–0.36 dL/g in N,N‐dimethylformamide (DMF) and 0.75 dL/g in H₂SO₄ at 25°C. The polyamides were generally soluble in a wide range of solvents, such as DMF, N,N‐dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, ethyl acetate, tetrachloroethane, hexamethylene phosphoramide, N‐methylpyrrolidone, and pyridine. Thermal analysis showed that these polyamides were practically amorphous, decomposed above 270°C, and exhibited 50% weight loss at and above 400°C. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

2-丁二酸单乙酯酰基-9,9-双甲氧甲基芴的制备

以芴为主要原料,经过醚化、酯化和Friedel-Crafts酰基化等反应,合成出了9,9-双羟甲基芴、9,9-双甲氧甲基芴、丁二酸单乙酯和丁二酸单乙酯酰氯4种中间体,并最终合成出目的产物2-丁二酸单乙酯酰基-9,9-双甲氧甲基芴。采用核磁共振对中间体和目的产物的结构进行了表征和分析。最后以2-丁二酸单乙酯酰基-9,9-双甲氧甲基芴为内给电子体合成出新型聚丙烯催化剂,采用丙烯液相本体聚合的方法,对催化剂催化丙烯聚合反应的性能进行了评价。     

9,9-双（甲氧基甲基）芴的合成及其应用研究

9,9-双（甲氧基甲基）芴（BMMF）的合成分两步进行：首先,在乙醇钠催化剂的作用下,芴与多聚甲醛反应合成了中间体9,9-双（羟甲基）芴（BHMF）,然后以四丁基溴化铵（TBAB）为相转移催化剂,再与氯甲烷发生烷基化反应合成了9,9-双甲氧基甲基芴。用9,9-双（羟甲基）芴作外给电子体进行了丙烯聚合应用,实验结果表明：9,9-双（甲氧甲基）芴（BMMF）是聚丙烯Ziegler-Natta催化体系较好的外给电子体。     

Synthesis and studies of blue light emitting polymers containing triphenylamine‐substituted fluorene and diphenylanthracene moiety

Photoluminescent (PL) polymers containing triphenylamine‐substituted fluorene and diphenylanthracene (DPA) units were synthesized by aromatic nucleophilic substitution reaction. The light emitting polymers (LEPs) contains hole‐transporting triphenylamine (TPA) groups at the C‐9 position of fluorene and DPA‐emitting segments in the main chain. The obtained polymers were soluble in various organic solvents and thermally stable. The synthesized polymers were successfully characterized by elemental analyses, FTIR and, ¹H NMR spectroscopy. The electrochemical measurements and optical properties of the polymers were also studied. The obtained polymers showed significant blue emission. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and properties of novel poly(coumarin‐amide)s

A novel monomer diacid, 6,6′‐methylenebis(2‐oxo‐2H‐chromene‐3‐carboxylic acid), was synthesized and used in a direct polycondensation reaction with various aromatic diamines in N‐methyl‐2‐pyrrolidone solution containing dissolved LiCl and CaCl₂, using triphenyl phosphite and pyridine as condensing agents to give a series of novel heteroaromatic polyamides containing photosensitive coumarin groups in the main chain. Polyamide properties were investigated by DSC, TGA, GPC, wide‐angle X‐ray scattering, viscosity, and solubility measurements. The copolymers were soluble in aprotic polar solvents, and their inherent viscosities varied between 0.49 and 0.78 dL g^?1. The weight‐average and number‐average molecular weights, measured by gel permeation chromatography, were 27,500–43,900 g mol^?1 and 46,500–66,300 g mol^?1, respectively, and polydispersities in the range of 1.48–1.69. The aromatic polyamides showed glass‐transition temperatures (T_g) ranging from 283 to 329°C and good thermal properties evidenced by no significant weight loss up to 380°C and 10% weight loss recorded above 425°C in air. All the polyamides exhibited an amorphous nature as evidenced by wide‐angle X‐ray diffraction and demonstrated a film forming capability. Water uptake values up to 3.35% were observed at 65% relative humidity. These polymers exhibited strong UV‐vis absorption maxima at 357–369 nm in DMSO solution, and no discernible photoluminescence maxima were detected by exciting with 365 nm. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of novel soluble fluorinated aromatic polyamides derived from fluorinated isophthaloyl dichlorides and aromatic diamines

Two series of fluorinated aromatic polyamides derived from two novel monomers, 5-(4-trifluoromethylphenoxy)isophthaloyl dichloride (3FPC) and 5-(3,5-bistrifluoromethyl-phenoxy)isophthaloyl dichloride (6FPC) with various aromatic diamines were synthesized and characterized. Experimental results indicated that the fluorinated aromatic polyamides showed good solubility in many organic solvents. The solubility of the polyamides was affected by the trifluoromethyl substituents and the pendent phenoxy groups in the polymer backbone. The fluorinated polyamides have good thermal stability with the glass transition temperature of 206-285 °C, the temperature at 5% weight loss of 442-460 °C in nitrogen. The polyamide films also exhibited good mechanical properties and excellent electrical and dielectric properties. The fluorinated groups in the polymer backbone have played an important role in the improvement of electrical and dielectric performance of polymer.     

9,9-双甲氧甲基芴的合成及其光谱分析

以芴为原料,在乙醇钠的催化下,经多聚甲醛羟甲基化反应合成了中间体9,9-双羟甲基芴,然后以四丁基溴化铵为相转移催化剂,再与氢氧化钠、碳酸二甲酯发生烷基化反应,合成了目标化合物。通过紫外光谱、红外光谱和核磁共振谱等分析测试手段对中间体和目标产物进行了结构表征并逐一归属。     

2,7-二溴-9-二烷硫基亚叉芴的合成及表征

以芴为起始原料,合成了2,7-二溴-9-二甲硫基亚叉芴、2,7-二溴-9-二十二烷硫基亚叉芴、2,7-二溴-9-二苄硫基亚叉芴和2,7-二溴-9-二硫代乙烯撑亚叉芴4种新的芴衍生物.所得产物的结构经IR,NMR表征.     

Synthesis and characterization of novel polymers derived from gluconolactone

A novel synthesis of vinyl monomers derived from D ‐gluconolactone, an interesting precursor obtained from D ‐glucose, is reported. The derivatization of D ‐gluconolactone is carried out by first reacting methacrylic acid with a diamine in water, followed by in situ amidation of the sugar compound. Three monomers containing different lengths of alkylamido groups between vinyl and sugar residues, have thus been obtained and homopolymerized with various free‐radical initiators. The resulting polymers were analysed by viscometry and were found to exhibit polyelectrolyte behaviour. Their structures were confirmed by NMR and consist of a predominantly syndiotactic structure. Copolymerization of the gluconamidoalkyl ammonium methacrylates with other hydrophilic monomers such as methacrylamide and vinylpyrrolidone was also achieved. © 2001 Society of Chemical Industry     

Preparation and characterization of novel polyamide paraffin MEPCM by interfacial polymerization technique

A novel polyamide‐paraffin microencapsulated phase change material (MEPCM) was prepared by interfacial polymerization technique using 1,3,5‐benzenetricarbonyl chloride (TMC) and ethylenediamine as monomers and 30# paraffin as core material. Morphology, chemical composition, thermal properties of the MEPCM were studied by scanning electron micrograph, FT‐IR spectrum, differential scanning calorimeter analysis and thermogravimetric analysis. The solvent resistances of the MEPCM were also studied by observing the morphology changes of the MEPCM under optical microscope. Results indicate that the MEPCMs prepared under optimal conditions have spherical shape with average diameter of 6.4 µm, and the polyamide shell has successfully packaged the paraffin core. The MEPCM has a high efficiency in storing and releasing heat. The latent heat is 121.7 J/g and the microencapsulation ratio is 87%, 5% weight loss temperature is 260°C. The MEPCM is stable in H₂SO₄ solution (ω = 0.98), NaOH solution (ω = 0.40), ethanol, acetone, ether, dimethylformamide while can be destroyed by ZnCl₂ solution (ω = 0.60). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci, 2013     

Synthesis and properties of polyamides from 2,5‐furandicarboxylic acid

The aim of this study is to investigate the synthesis of 2,5‐furandicarboxylic acid (FDCA)‐based copolyamides. Indeed, FDCA monomer may be a potential bio‐based alternative to phthalic acids. A series of polyamides and copolyamides, PA 6‐I(x)/6‐F(y), are synthesized in a pilot scale reactor by melt polycondensation of salts based on FDCA, isophthalic acid (IPA), and 1,6‐hexamethylenediamine. The chemical structure and composition of the resulting copolymers are extensively characterized by NMR (¹H, ¹³C, and 2D), MALDI‐TOF as well as size exclusion chromatography and solution viscosimetry. Their thermal properties are studied by differential scanning calorimetry and TGA and also by a molecular modeling technique. It is pointed out that, during the synthesis, FDCA‐rich polymers overcome a massive decarboxylation of FDCA, preventing the production of high molar mass polymers. It is also found that all polymers are amorphous and that the glass transition temperatures decrease as the amount of FDCA in the polymer increases. This is confirmed by the results from molecular dynamics. In addition, it is observed that the copolymers become more hygroscopic when the amount of FDCA in the copolyamides increases. However, the water uptake of PA 6‐I(x)/6‐F(y) with 90 > x > 50 is lower than those of PA6 and PA 66 polyamides. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45901.     

Synthesis and properties of novel soluble polychloro substituted aromatic polyamides

A novel monomer of tetrachloroterephthaloyl chloride (TCTPC) was prepared by the chlorination of terephthaloyl chloride catalyzed by ferric chloride at 175–180°C for 10 h, and confirmed by FTIR, MS, and elemental analysis. A series of new polychloro substituted polyamides with inherent viscosities of 1.17–1.28 dL/g have been prepared from TCTPC with various aromatic diamines. All the polyamides were amorphous and readily soluble in polar solvents such as NMP, DMAc, DMF, and DMSO at room temperature, and could afford flexible and tough films via solution casting. The cast films exhibited good mechanical properties with tensile strengths of 83.6–106.8 MPa, elongations at breakage of 3.9–7.1%, and tensile modulus of 2.28–3.98 GPa. These polyamide films also exhibited good thermal stability with the glass transition temperature of 250–284°C, the temperature at 5% weight loss of 470–504°C and high char yields of 57.8–59.7% in nitrogen. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of a novel 3D copper(I) coordination polymer with a ligand generated in situ

Hydrothermal reaction of CuCl₂ · 2H₂O, NaN₃ with 1,4-dicyanobenzene in water/ethanol yielded a novel Cu(I)-tetrazolate, {Cu(cptz)}_n, (1) (Hcptz is 5-(4-cyanophenyl)-tetrazole). The cptz ligand in the complex was generated in situ through the [2 + 3] cycloaddition reaction involving one of the two cyano-groups of the precursor 1,4-dicyanobenzene. The structure characterization shows that 1 possesses a 3D 4-connected SrAl₂ topological network. Additionally, complex 1 exhibits strong yellow fluorescence at room temperature in the solid state.     

Synthesis and characterization of new polyamides derived from 1,3‐(4‐carboxy phenoxy) propane and aromatic diamines

Six new polyamides 5a‐f containing flexible trimethylene segments in the main chain were synthesized through the direct polycondensation reaction of 1,3‐(4‐carboxy phenoxy) propane 3 with six derivatives of aromatic diamines 4a‐f in a medium consisting of N‐methyl‐2‐pyrrolidone, triphenyl phosphite, calcium chloride, and pyridine. The polycondensation reaction produced a series of novel polyamides containing flexible trimethylene segments in the main chain in high yield with inherent viscosities between 0.32 and 0.68 dL/g. The resulted polymers were fully characterized by means of FTIR spectroscopy, elemental analyses, inherent viscosity, and solubility tests. Thermal properties of these polymers were investigated by using thermal gravimetric analysis (TGA) and differential thermal gravimetric (DTG). The glass‐transition temperatures of these polyamides were recorded between 165 and 190°C by differential scanning calorimetry, and the 10% weight loss temperatures were ranging from 360 to 430°C under nitrogen. 1,3‐(4‐Carboxy phenoxy) propane 3 was prepared from the reaction of 4‐hydroxy benzoic acid 1 with 1,3‐dibromo propane 2 in the presence of NaOH solution. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and the magnetic properties of novel metal(II) complexes of polyamides

Novel polyamides DTPA and DTPyA are prepared from 2,2′-diamino-4,4′-bisthiazole and aromatic polycarbonyl chloride. The complexes of Fe(II) and Cu(II) metal of the polyamides are also prepared. The complexes as well as the polyamides are characterized through IR and EPR, and the magnetic property of each complex are measured through MPMS. It is found the Fe(II) complexes of both DTPA and DTPyA reveal magnetization ability, especially the Fe(II) DTPA complex. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 818–822, 2001     

水杨醛缩邻甲苯胺Schiff碱及其Zn(Ⅱ)配合物的合成与表征

由水杨醛和邻甲苯胺缩合形成的不对称Sch iff碱与Zn(Ⅱ)盐反应得到了金属配合物。通过元素分析、红外光谱、紫外-可见光谱、核磁共振氢谱(1H NMR)及13C谱(13C NMR)等分析测试手段对配体及其配合物进行了结构表征,确定了配合物的可能结构,结果表明,配体通过N,O原子与金属离子配位。