Two types of aggregation structure formed in a thermotropic aromatic polyester

The aggregation structures of the enantiotropic liquid crystalline polyester, K145N213 (°C), were investigated using polarizing optical microscope (POM), wide-angle X-ray diffraction (WAXD) and scanning electron microscope (SEM). Depending on annealing temperature, two types of aggregation structure (AS), I and II, were formed. AS I was grown directly from nematic melt, while AS II was formed from supercooled liquid crystalline state. By comparing AS I and AS II it was found that there was much difference between them, such as the morphology, the melting behaviour and the pattern of WAXD. The experimental results showed that the aggregation behaviour of AS II was more like that of the conventional crystalline polymers, while AS I made conspicuous difference. A sketch map of the formation mechanism of AS I was suggested, which showed that the particular AS I was composed of nematic domains.     

Orientational order and mechanical properties of poly(amide-block-aramid) alternating block copolymer films and fibers

Mechanical properties and orientational order of a series of uniaxially oriented block copolymer films and fibers comprised of alternating rigid aramid blocks of poly(p-phenylene terephthalamide) (PPTA) and flexible blocks of polyamide 6,6 (PA 6,6) have been investigated. The prepared block copolymer films differ in aramid content and average block length. The films were prepared by shearing the polymer solutions (in sulphuric acid) followed by rapid coagulation of the solutions in water. From wide angle X-ray scattering (WAXS) and optical polarisation microscopy (OPM) it was found that films with a mole fraction of PPTA of at least 0.5 show a liquid crystalline (LC) phase. It was found that the mechanical properties of LC block copolymer films are similar to the properties of isotropic films, as determined with dynamical mechanical analyses (DMAs) and from tensile tests. This was attributed to the relative low parameter of the LC films obtained by using WAXS. Copolymerisation of the PPTA blocks with the flexible polyamide blocks resulted in an increase of storage and Young's modulus, a decrease of the elongation at break while the tensile strength was unaffected compared to normal PA 6,6. Block copolymer fibers have been spun from liquid crystalline solutions by means of a dry-jet wet spinning process. The only variable parameter was the imposed draw-ratio in the air-gap of the spinning process. Increasing the draw-ratio resulted in an increased molecular orientation, Young's modulus and tensile strength of the fibers while its effect on the maximum elongation at break was small. Heat treatment at 300 °C of the fibers resulted in an increase of the Young's modulus, a minor increase of the strength and a decrease of the elongation at break. Scanning electron microscopic (SEM) photographs of the fractured surfaces of the block copolymer fibers do not show a fibrillar fracture surface, which is typically observed for pure PPTA fibers.     

新型芳香族聚酯多元醇的合成与性能研究

用对苯二甲酸、苯酐、二元醇、三元醇等多元醇为原料制备新型芳香族聚酯多元醇,考察了聚酯多元醇酸值、羟值与其醇酸摩尔比的关系,以及酸值与反应时间的关系,并将其用于制备硬质聚氨酯泡沫塑料,讨论了新型聚酯多元醇对硬质聚氨酯泡沫塑料的性能影响。     

Effect of a fluorine lateral moiety on the liquid crystallinity of wholly aromatic polyester-amides

We have identified the effect of a fluorine lateral moiety on the liquid crystallinity of wholly aromatic polyester-amides. The evolution of liquid crystal texture for two reaction systems, p-acetoxybenzoic acid (ABA)/acetoxy acetanilide (AAA)/3-fluorophthalic acid (FPA) and ABA/AAA/phthalic acid (PA), were examined and compared by in situ polymerizations under a polarizing microscope with a heating-stage. The fluorine lateral moiety was found to have an adverse effect on the liquid crystallinity. The system containing FPA needs higher critical ABA content (the rigid and straight monomer) to form liquid crystallinity than the system containing PA. In addition, the LC phase emerges faster in the ABA/AAA/PA system than in the ABA/AAA/FPA system during polymerizations. Amorphous phase reappears in the later stage of thin film polymerizations for both systems if ABA content is in a particular range. However, the ABA/AAA/FPA system has a greater amorphous area than the ABA/AAA/PA system.     

Synthesis and characterization of aromatic copolyesters containing siloxane linkages in the polymer backbone

A new series of aromatic copolyesters containing siloxane linkages were prepared by the melt polymerization of bisphenol A (BPA) with eugenol end‐capped siloxane (EuSi), diphenyl terephthalate (DPT), and diphenyl isophthalate (DPI) in varying ratio in the temperature range 220–290°C under reduced pressure in the presence of dibutyl tin dilaurate (DBTL) catalyst. The siloxane copolyesters prepared were characterized by FTIR, ¹H‐NMR spectroscopy, solution viscosity, thermogravimetric analysis, differential scanning calorimetry, and X‐ray diffraction. The effect of incorporation of eugenol end‐capped siloxane was studied on the properties of BPA/DPI/DPT copolyesters. The glass‐transition temperature of copolyester was decreased from 184 to 70°C by incorporation of 20% of eugenol end‐capped siloxane. All copolyesters were found to be soluble in commonly used aprotic polar solvents and had film‐forming properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3222–3228, 2006     

Synthesis and characterization of aromatic polyesters and copolyesters from 4,4′‐(1‐hydroxyphenylidene)diphenol and 4,4′‐(9‐fluorenylidene)diphenol

Two isophthalic polyesters from 4,4′‐(1‐hydroxyphenylidene)diphenol (BAP/ISO) and 4,4′‐(9‐fluorenylidene)diphenol (BF/ISO), and three different copolyesters containing 75, 50, and 25 mol % of BAP/ISO were synthesized by interfacial polycondensation. This preparation method yielded polymers and copolymers that produced flexible and transparent films when they were cast from solution. Proton NMR spectrometry studies showed that the isophthalic copolyesters were obtained as random copolymers with differences in comonomer composition no larger than 2.5 mol % with respect to the expected compositions. Wide‐angle X‐ray diffraction measurements indicated that all the polyesters and copolyesters were amorphous. The copolyesters showed amorphous patterns with maxima that fell between those of the polyesters. It was also found that thermal properties such as glass‐transition temperature, onset of decomposition temperature, thermal stability, dynamic mechanical storage modulus, and maximum on the α‐transition of the damping factor tan δ of BF/ISO were higher than those of BAP/ISO. The values of these thermal properties in the copolyesters fell between those of the polyesters and were dependent on the amounts of BF/ISO and BAP/ISO present in the copolyester in a linear fashion. Therefore, the thermal properties of a given copolyester can be predicted directly from the comonomers' composition. Overall, it shows that the interfacial polycondensation method is suitable to obtain these copolyesters in a controlled manner and that their properties can be tailored to be between those of the homopolyesters. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2515–2522, 2002     

芳香醇的合成

通过Cannizzaro反应,以芳香醛和甲醛为原料,合成系列芳香醇。研究了反应物的摩尔比、催化剂氢氧化钾的质量分数及用量、反应时间等因素对芳香醇收率的影响。在n(芳香醛)∶n(甲醛)=1.0∶1.5,质量分数40%KOH溶液的用量1.5 mL,室温下搅拌反应50 min的优化条件下,芳香醇的产率为73.4%~97.8%。     

Phosphine oxide containing aromatic polyester

A phosphine oxide containing aromatic polyester has been synthesized by the direct polycondensation reaction of bis[4-(m-carboxyphenoxy)phenyl]phenylphosphine oxide (m-BCPPO) and 4,4′-isopropylidene-diphenol (bisphenol A). The presence of phosphine oxide linkages in the backbone gives this polymer superior properties: namely thermo-oxidative stability, high char yield and solubility in common organic solvents.     

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     

Electrokinetic properties of modified polyester fibers

Electrokinetic properties of normal polyester flat filament, texturized polyester and cationic dyeable polyester were studied when solutions of different pH and cationic dye concentrations were run through them. The textured polyester exhibited maximum negative zeta potential whereas cationic dyeable polyester showed minimum. The negative zeta potential was found to be maximum near neutral pH. The effect of heat-setting at extreme conditions (220°C, 90 s) on electrokinetic properties was also studied. Such heat-setting was found to lower negative zeta potential, attributed to a decrease in surface area. Cationic dyeable, “easy” dyeable, and normal flat filament type polyester were also investigated. Results with respect to negative zeta potential, surface charge density, and surface conductivity, are discussed. © 1993 John Wiley & Sons, Inc.     

Synthesis,characterization, and thermal properties of phosphorus‐containing,wholly aromatic thermotropic copolyesters

A series of phosphorus‐containing, wholly aromatic thermotropic copolyesters from acetylated 2‐(6‐oxide‐6H‐dibenz〈c,e〉〈1,2〉oxa phosphorin‐6‐yl)‐1,4‐dihydroxy phenylene, p‐acetoxybenzoic acid, terephthalic acid, and isophthalic acid were prepared by melting polycondensation. The structure and basic properties of the polymers, such as the glass‐transition temperature (T_g), melting temperature (T_m), thermal stability, crystallinity, and liquid crystallinity, were investigated with Fourier transform infrared, elemental analysis, differential scanning calorimetry (DSC), thermogravimetric analysis, wide‐angle X‐ray diffraction, and hot‐stage polarizing optical microscopy. The copolyesters had relatively high T_g values ranging from 183 to 192°C. The T_m values obtained from DSC curves for samples P‐20 and P‐25 were 290 and 287°C, respectively (where the number in the sample name indicates the molar fraction of the phosphorus‐containing monomer in the reactants). The initial flow temperatures of other samples observed with hot‐stage polarizing microscopy were 271–290°C. The 5% degradation temperatures in nitrogen ranged from 431 to 462°C, and the char yields at 640°C were 41–52%. All the copolyesters, except P‐40, were thermotropic and nematic. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1278–1284, 2002     

Synthesis, thermal and optical properties of liquid crystalline terpolymers containing azobenzene and dye moieties

The synthesis, thermal properties and photochemical and photophysical studies of new azopolymers are described. These polymers contain three different types of monomer, each of which is mainly responsible for a particular function: A mesogenic benzanilide, a photochromic azobenzene and a dye unit (a benzoxazole, an anthracene or a stilbene derivative). This approach provides liquid crystalline terpolymers with different spectral properties and with the potential ability to be photoaligned by irradiation and thermotropic self-organization. The polymers have been prepared by random radical polymerisation of the corresponding methacrylate-fucntionalised units. All of the materials show good thermal stability and liquid crystalline behaviour, displaying smectic A or nematic mesophases. Optical properties of the polymers in solution display additive bands in the absorbance spectrum and luminescent properties in the emission region of the individual dye monomers. However, films of these polymers are not luminescent. A study of the absorption and redox properties of the dyes has been performed in order to evaluate the quenching process in the polymers.     

Ethynyl aromatic siliconhybridized resin: Synthesis,characterizations, and thermal properties

A novel silicon‐containing resin (ESA resin) was successfully synthesized by the condensation reaction of lithium arylacetylide with chlorosilane in high yields. The resin was characterized by the techniques of FTIR, ¹H‐NMR, ²⁹Si‐NMR, and gel permeation chromatography. Thermal cure process was monitored by DSC and FTIR methods. This resin could melt at around 100°C and thermally cured at 200–250°C with low exothermal enthalpy. Owing to the high aryl groups containing and the complete crosslinking of ethynyl groups, the cured ESA resin exhibited excellent thermal stability and high char yield. The decomposition temperature $T_{d_5}$ of the cured resin was at 510°C, and the residue yield at 900°C was 82.9% in N₂. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

含芳醚腈链段的双邻苯二甲腈树脂的合成与性能

合成了一系列含芳醚腈链段的双邻苯二甲腈,以2,6-二-4-氨基苯氧基苯甲腈为交联剂获得了相应的预聚树脂。采用FTIR,1H NMR和13C NMR对合成的双邻苯二甲腈的结构进行了表征,并通过DSC及TGA分析研究了预聚物的固化性能和耐热性。结果表明,该类树脂熔融流动温度在60℃左右,固化反应温度在220℃左右,加工温度范围得以有效提高。其固化物在空气和氮气气氛下的起始分解温度均高于460℃,表明固化物具有较高的热稳定性和热氧稳定性。     

芳香族聚酰胺纤维生产技术与应用

叙述了芳香族聚酰胺纤维的制备、结构性能、产品应用、技术发展趋势等,并对间位芳香族聚酰胺纤维和对位芳香族聚酰胺纤维产品进行了重点的描述,提出了发展我国芳香族聚酰胺纤维产业相关的对策和建议。     

芳香族聚酯纤维弯曲回弹性能研究

研究了PTT ,PET和PBT纤维的弯曲回弹性能及回复机理。结果表明 :在形变时间 2 0min条件下 ,PBT纤维的弯曲回弹率最高 ,PTT纤维次之 ,PET纤维最低 ,且均随回复时间的延长而提高。弯曲回弹率与其断裂比功之间均存在明显的相关性 ,随着纤维中亚甲基数的增加 ,断裂比功降低 ,弯曲回弹率提高。纤维弯曲回弹性能与其聚集态结构中的结晶和取向结构 ,以及结晶结构中大分子链的构象有关     

Synthesis and randomization of well-defined sequence,wholly aromatic copolyester/esteramides

Well-defined sequence, wholly aromatic copolyester/esteramides have been synthesized by an interfacial polycondensation of a preformed triad diacid chloride monomer, di(para-chlorocarbonylphenyl)isophthalate, with the disodium salt of hydroquinone or of deuterated hydroquinone, or with meta-phenylene diamine. Carbon-13 nuclear magnetic resonance (NMR) spectroscopy provided unequivocal evidence for regularly alternating polymer structures, and coupled with statistical methods, for randomization on heating in the case of regularly alternating poly(p-oxybenzoate-co-p-phenylene isophthalate). Polymers synthesized using standard high-temperature melt-polymerization techniques were shown by statistical/carbon-13 NMR methods to have essentially random structures. Thermal properties of copolymer powders and films were found to vary with monomer sequence distribution as well as with composition. © 1994 John Wiley & Sons, Inc.     

Structures and properties of easily dyeable copolyesters and their fibers respectively modified by three kinds of diols

Three kinds of modified poly(ethylene terephthalate) copolyesters were synthesized, using sodium‐5‐sulfo‐bis‐(hydroxyethyl)‐isophthalate as the third monomer, 1,3‐propanediol (PDO), 2‐methyl‐1,3‐propanediol (MPD), and 2,2‐dimethyl‐1,3‐propanediol (neopentyl glycol or NPG) as the fourth monomer, respectively. The copolyester fibers were also prepared by melt spinning and drawing processes. The effect of PDO, MPD, and NPG on the synthesis and spinning process was investigated, and the structures and properties of both copolyesters and the produced fibers were characterized. The results exhibited that the structural difference of PDO, MPD, and NPG played an important role in the synthesis and spinning process, and significantly affected the structures and properties of both copolyesters and the produced fibers, which thereby resulted in the difference in terms of dyeability improvement of copolyester fibers. The dyeing at boiling temperature under normal pressure experiments of copolyester fibers in both disperse dyebath and cationic dyebath revealed that incorporation of the fourth monomer could improve the dyeability of copolyester fiber, and copolyester fiber containing MPD unit had better dyeability due to a looser, more accessible structure when compared with the fiber containing PDO or NPG unit. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and characterization of blends containing natural and some synthetic rubbers with synthesized aromatic polyester

This work deals with the synthesis of aromatic polyester (AP) from polyarylate [Bisphenol A (BPA)/dimethyl terephalate (DMT)/ethylene glycol (EG)] and maleic anhydride (MA) in presence of dibutyl tin oxide (DBTO) as a catalyst. Blends were prepared from candidated AP (10–30 phr) with different types of rubber [natural rubber (NR), acrylonitrile butadiene rubber (NBR), styrene butadiene rubber (SBR) and ethylene‐propylene‐diene monomer (EPDM)]. The obtained blends were subjected to physicomechanical measurements to evaluate their properties as efficient blends for economic industrial applications. In case of AP blended with rubber, better properties were obtained than that of rubber vulcanizates. The fatigue life values decreases by increasing the AP contents for all types of the tested blends. The equilibrium swelling (%) for the prepared blends exhibits different behavior in solvents like toluene and motor oil. The addition of N‐isopropyl‐N′‐phenyl‐p‐phenylene diamine (IPPD), as antioxidant, affects the properties of all the prepared products. These properties were in consequent with the data of the initial shear modulus, which is calculated from the Mooney‐Rivlin equation and the percentage of the equilibrium swelling. Scanning electron microscope (SEM) was used to study the morphological structure; the SEM results show the changes in surface of the rubber before and after being blended with AP. The investigated blends are considered a new trend in giving products with variable physicomechanical characteristics. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of wholly aromatic polyamides containing pendent amino and cyano groups

The new pyrazole-ring containing diamine monomer with amino and cyano groups, 1,3-di-p-aminophenyl-4-cyano-5-aminopyrazole (PYA), was prepared from 4-nitrobenzoyl chloride and 4-nitrophenyl hydrazine with 4 steps. The monomer was converted to polyamides with terephthaloyl chloride and isophthaloyl chloride. The amino and cyano groups on the pyrazole-ring were not affected during polymerization. The synthesized polyamides having intrinsic viscosities of 0.92 – 1.18 dL/g were amorphous, and soluble in polar aprotic solvents and boiling acetone and THF. The polymers had high glass transition temperatures and high thermal stability. 5% weight loss temperatures in nitrogen occurred around 490 °C, but these polymers are partially degraded at 300 °C in air due to the amino group on the pyrazole-ring. Received: 6 March 1997/Accepted: 1 April 1997