Main‐chain liquid crystalline poly(ester‐amide)s containing lithocholic acid units

A series of poly(ester‐amide)s based on an ester group containing lithocholic acid derivative [3‐(3‐carboxypropionyl) lithocholic acid] and several aromatic diamines (naphthalene‐1,5‐diamine, 4,4′‐diaminodiphenyl ether, 4,4′‐diaminodiphenylmethane, 4,4′‐diaminodiphenylsulfone, benzidine, m‐phenylenediamine, p‐phenylenediamine, and tetraphenylthiophene diamine) was synthesized and characterized by solubility, viscosity, IR, differential scanning calorimetry, thermogravimetric analysis, and optical microscopy. The polymers were soluble in most of the organic solvents and had inherent viscosities in the range of 0.21–0.38 dL/g. All the polymers exhibited a nematic mesophase, but only on shearing. Thermal transitions due to mesophase formation were not seen in the differential scanning calorimetry thermograms. However, the liquid crystalline character of the polymers was observed under an optical microscope. Thermogravimetric analyses revealed the maximum decomposition temperature was 390–435°C for these polymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 73–80, 2006     

Synthesis of biodegradable amino‐acid‐based poly(ester amide)s and poly(ether ester amide)s with pendant functional groups

A new family of biodegradable amino‐acid‐based poly(ester amide)s (AA–PEAs) and amino‐acid‐based poly(ether ester amide)s (AA–PEEAs) consisting of reactive pendant functional groups (? COOH or ? NH₂) were synthesized from unsaturated AA–PEAs and AA–PEEAs via a thiol–ene reaction in the presence of a radical initiator (2,2′‐azobisisobutyronitrile). The synthetic method was a one‐step reaction with near 100% yields under mild reaction conditions. The resulting functional AA–PEA and AA–PEEA polymers were characterized by Fourier transform infrared spectroscopy, NMR, and differential scanning calorimetry. These new functional AA–PEA and AA–PEEA derivatives had lower glass‐transition temperatures than the original unsaturated AA–PEA and AA–PEEA polymers, and their solubility in some organic solvents also improved. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Hydrogen bonds in poly(ester amide)s and their model compounds

The hydrogen bonds in poly(ester amide)s and their model compounds were investigated using infra-red spectroscopy in the temperature range from 20 to 240°C. It was found that in the polymers investigated both amide—amide and amide—ester hydrogen bonds were formed, while in the corresponding model compounds only amide-amide hydrogen bond formation was observed.     

Toughening of poly(propylene carbonate) by hyperbranched poly(ester‐amide) via hydrogen bonding interaction

Poly(propylene carbonate) (PPC) is a biodegradable alternative copolymer of propylene oxide and carbon dioxide. As an amorphous polymer with lower glass transition temperature around 35 °C, PPC shows poor mechanical performance in that it becomes brittle below 20 °C and its dimensional stability deteriorates above 40 °C; thus toughening of PPC is urgently needed. Here we describe a biodegradable hyperbranched poly(ester‐amide) (HBP) that is suitable for this purpose. Compared with pure PPC, the PPC/HBP blend with 2.5 wt% HBP loading showed a 51 °C increase in thermal decomposition temperature and a 100% increase in elongation at break, whilst the corresponding tensile strength remained as high as 45 MPa and tensile modulus showed no obvious decrease. Crazing as well as cavitation was observed in the scanning electron microscopy images of the blends, which provided good evidence for the toughening mechanism of PPC. The intermolecular hydrogen bonding interaction confirmed by Fourier transform infrared spectral analysis proved to be the reason for the toughening phenomenon. Copyright © 2011 Society of Chemical Industry     

聚丙烯/聚醚酯酰胺共混纤维的研制

用聚乙二醇与己二酸反应合成聚醚酯,再用聚醚酯与己内酰胺反应得到聚醚酯酰胺。将聚醚酯酰胺与聚丙烯共混并纺丝得到聚丙烯/聚醚酯酰胺共混纤维;研究了聚醚酯与聚醚酯酰胺的结构和热性质;考察了共混纤维性能。结果表明:聚醚酯含量增加,聚醚酯酰胺的熔点下降,结晶温度升高;共混纤维的抗静电性和回潮率随聚醚酯酰胺含量和聚醚酯含量的增加而增强;共混纤维有很好的可染性,但强度略低。     

Effects of p‐hydroxybenzoic acid monomer units on physical properties of thermal liquid crystalline poly(ester imide ketone)s

A series of poly(ester imide ketone)s (PEIKs) with varied p‐hydroxybenzoic acid (HBA) molar fraction derived from N,N′‐hexane‐1,6‐diylbis(trimellitimide), 4,4′‐dihydroxybenzophenone, and p‐hydroxybenzoic acid were synthesized by a “step‐feeding” polycondensation method in benzene sulfonyl chloride, dimethylformamide, and pyridine. High field ¹H, ¹³C, and 2D NMR spectroscopy measurements were combined to determine the assignments of hydrogen and carbon atoms in the copolymers. ¹³C inverse gated decoupling NMR spectra were taken and used as a quantitative method to analyze the chain sequence structures of these copolymers. The liquid crystalline behaviors and thermal properties of the PEIKs were characterized by polarized light microscopy (PLM), wide‐angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The NMR studies show that the monomeric unit ratios of the PEIKs are very close to the ratios of the monomers added into the polycondensation process. The analytical results of sequence distribution indicate that the sequence ratios of I‐H, H‐D, and H‐H dias rise with the increase of HBA molar fraction, while that of I‐D decrease. It is worth noting that the sequence ratios of H‐H are always very small among the four sequence ratios although the HBA molar fraction varied from 0 to 50%. It was shown that the copolymers possess a typical nematic thermotropic liquid crystalline character and high thermal stability, which is strongly related with the changes in sequence structure of the molecular chains. This type of liquid crystalline polymers also exhibits excellent fiber‐forming character in the melting state, which would find its potential usages in high performance fiber and fiber modification materials. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3183–3193, 2007     

Incorporation of different crystallizable amide blocks in segmented poly(ester amide)s

High molecular weight segmented poly(ester amide)s were prepared by melt polycondensation of dimethyl adipate, 1,4-butanediol and a symmetrical bisamide-diol based on ε-caprolactone and 1,2-diaminoethane or 1,4-diaminobutane. FT-IR and WAXD analysis revealed that segmented poly(ester amide)s based on the 1,4-diaminobutane (PEA(4)) give an α-type crystalline phase whereas polymers based on the 1,2-diaminoethane (PEA(2)) give a mixture of α- and γ-type crystalline phases with the latter being similar to γ-crystals present in odd-even nylons. PEA(2) and PEA(4) polymers with a hard segment content of 25 or 50 mol% have a micro-phase separated structure with an amide-rich hard phase and an ester-rich flexible soft phase. All polymers have a glass transition temperature below room temperature and melt transitions are present at 62-70 °C (T_m,1) and at 75-130 °C (T_m,2) with the latter being highest at higher hard segment content. The two melt transitions are ascribed to melting of crystals comprising single ester amide sequences and two or more ester amide sequences, respectively. These polymers have an elastic modulus in the range of 159-359 MPa, a stress at break in the range of 15-25 MPa combined with a high strain at break (590-810%). The thermal and mechanical properties are not influenced by the different crystalline structures of the polymers, only by the amount of crystallizable hard segment present.     

Gas foaming of segmented poly(ester amide) films

Biodegradable segmented poly(ester amide)s, based on dimethyl adipate, 1,4-butanediol and N,N′-1,2-ethanediyl-bis[6-hydroxy-hexanamide], with two distinct melting transitions were gas foamed using carbon dioxide (CO₂). Polymer films were saturated with CO₂ at 50 bar for 6 h after which the pressure was released. The samples were immersed in octane at the desired temperature after which foaming started immediately. Just above the lower melt transition the polymers retain adequate mechanical properties and dimensional stability, while the chain mobility increased sufficiently to nucleate and expand gas cells during the foaming process. In this way semi-crystalline poly(ester amide)s can be gas foamed below the flow temperature.Two poly(ester amide)s with 25 mol% (PEA2,5-25) and 50 mol% (PEA2,5-50) of bisamide segment content were foamed at 70 and 105 °C, respectively. The storage modulus (G′) of both pure polymers at the onset foaming temperature is 50-60 MPa. Closed-cell foams were obtained with a maximum porosity of ∼90%. The average pore size of PEA2,5-25 ranges from 77 to 99 μm. In contrast, the average pore size of PEA2,5-50 is in between 2 and 4 μm and can be increased to 100 μm by lowering the CO₂ saturation pressure to 20 bar. The porosity of PEA2,5-50 foams using this saturation pressure decreased to 70%.     

含锌聚醚酯酰胺的热性能研究

以氧化锌、脂肪族二羧酸、聚乙二醇为原料合成含锌聚醚酯(PEEM),再将PEEM与聚己内酰胺低聚合物反应,制备含锌聚醚酯酰胺(PEEAM),借助差示扫描量热法(DSC)、热重(TG)分析,研究了PEEAM的热性能。结果表明:PEEAM呈双熔融和双结晶峰,随PEEM含量增加,PEEAM中PEEM链段的熔融温度降低,熔融热焓增大,聚酰胺链段的熔融温度略有下降,结晶放热和结晶温度随PEEM含量变化有最小值;PEEAM中含脂肪族二羧酸种类不同,其相应的熔融温度、熔融热焓、结晶温度及结晶放热不同,没有明显规律可循。脂肪族二羧酸种类对PEEAM的初始降解温度和最大质量损失温度没有明显影响。PEEM含量增大,PEEAM的热失重速率增大。     

Studies on the biodegradation and biocompatibility of a new poly(ester amide) derived from L-alanine

A new poly(ester amide) derived from L -alanine has been synthesized and characterized. The polymer has good fiber- and film-forming properties, as well as other characteristics like thermal stability and solubility in chloroform, which enhance its processing facilities. Degradation studies show that both pH and temperature influence in the hydrolisis rate that takes mainly place through the ester linkages. Degradation was also studied by using different enzymes. Results indicated that papain was the most efficient of these, and that the hydrolysis to water-soluble products could be attained in a few days. Basal cytotoxicity was assayed using a mouse L929 fibroblast permanent cell line. The MTT viability test was performed with liquid extract of the material (50 days, 37°C). An attachment and proliferation screening study with intact material was also carried out. No cytotoxic responses were detected, in either assay, after a 24- and 48-h incubation period with the cells. After 72 h a slight cytotoxicity was detected in the polymer material, while a more significant one was detected in the material extract. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1537–1549, 1998     

Synthesis and characterization of poly(ester amide)s containing crystallizable amide segments

High molecular weight segmented poly(ester amide)s were prepared by melt polycondensation of 1,4-butanediol, dimethyl adipate and a preformed bisamide-diol based on 1,4-diaminobutane and ε-caprolactone. By varying the ratio of the bisamide-diol and 1,4-butanediol, a series of polymers was obtained with a hard segment content between 10 and 85 mol%. FT-IR and WAXD analysis revealed that the poly(ester amide)s crystallize in an α-type phase similar to the α-phase of even-even nylons. These polymers all have a micro-phase separated structure with an amide-rich hard phase and an ester-rich flexible soft phase. The polymers have a low and a high melt transition, corresponding with the melting of crystals comprising single ester amide sequences and two or more ester amide sequences, respectively. The low melt transition is between 58 and 70 °C and is independent of polymer composition. By increasing the hard segment content from 10 to 85 mol% the high melt transition increased from 83 to 140 °C while the glass transition temperature increased from −45 to −5 °C. Likewise, the elastic modulus increased from 70 to 524 MPa, the stress at break increased from 8 to 28 MPa while the strain at break decreased from 820 to 370%. Thermal and mechanical properties can thus be tuned for specific applications by varying the hard segment content in these segmented polymers.     

以季戊四醇为核的超支化不饱和聚酰胺酯的合成

以顺丁烯二酸酐（MA）和二乙醇胺（DEA）为原料合成超支化不饱和聚酰胺酯AB2型单体。通过季戊四醇和AB2型单体进行酯化反应合成支化不饱和聚酰胺酯HBP。考查了反应温度、催化剂用量、反应时间对反应产率的影响。最佳工艺条件为：温度140℃,反应时间5h,催化剂对甲苯磺酸用量为反应物量的1.5%。     

Synthesis and characterization of thermotropic liquid crystalline poly(ester‐imide‐ketone)

A series of poly(ester imide ketone)s derived from N,N′‐hexane‐1,6‐diylbis(trimellitimide), 4,4′‐dihydroxybenzophenone, and p‐hydroxybenzoic acid (PHB) were synthesized by the direct polycondensation method in benzene sulfonyl chloride, dimethylformamide, and pyridine with varied PHB contents. The liquid crystalline behavior and thermal properties of the poly(ester imide ketone)s were characterized by polarized‐light microscopy, wide‐angle X‐ray diffraction, thermogravimetric analysis, differential scanning calorimetry, and temperature‐modulated differential scanning calorimetry (MDSC). The results showed that the synthesized polymers possessed a nematic thermotropic liquid crystalline characteristic and high thermal stability. The liquid crystalline polymers, with a PHB content ranging from 0 to 50 mol %, exhibited multiple phase transitions as evidenced by the MDSC results. A transitional smectic phase from solid state to nematic thermotropic liquid crystalline state was observed, and a transition model is proposed. Under certain conditions, the polymer with 33 mol % PHB content showed two significantly different liquid crystalline textures. This type of liquid crystalline polymer exhibited excellent fiber forming. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1045–1052, 2003     

Miscibility in blends of liquid crystalline poly(p-oxybenzoate-co-p-phenyleneisophthalate) and polyarylate

The miscibility of liquid crystalline poly(p-oxybenzoate-co-p-phenyleneisophthalate) (HIQ35) and polyarylate (PAr) coprecipitated from a mixed solvent of phenol/tetrachloroethane was investigated with differential scanning calorimetry. It was found that the amorphous phase of HIQ35 and PAr formed a partially miscible blend at low concentration of HIQ35. No measurable interaction between HIQ35 and PAr occurred when the weight fraction of HIQ35 was close to or less than that of polyarylate, as evidenced by wide-angle X-ray diffraction results. Upon annealing at 315°C for several minutes, the apparent miscibility of HIQ35 with polyarylate appeared as a result of an initial reaction between the polymers. For longer annealing time, the thermal degradation of HIQ35 joined in the reaction. This reaction or degradation in the blend was confirmed by nuclear magnetic resonance analysis and the intrinsic viscosity measurement of the blend. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1581–1589, 1998     

超支化聚酰胺酯对聚乳酸增韧改性的研究

采用熔融共混的方法,用生物可降解的超支化聚酰胺酯(HBP)对聚乳酸(PLA)进行增韧改性,制备出具有良好韧性的PLA复合材料。对不同HBP含量的共混物的红外光谱、热性能和力学性能进行了测试和分析。红外光谱显示PLA和HBP间存在氢键作用。HBP的加入使PLA的结晶度从30.99%降低到18.58%。当HBP含量增加到10%时,PLA共混物的拉伸强度略有提高,且断裂伸长达到43.06%。结果表明:HBP的加入对PLA起到了很好的增韧作用。     

Rheological properties in blends of poly(aryl ether ether ketone) and liquid crystalline poly(aryl ether ketone)

Rheological properties of the blends of poly(aryl ether ether ketone) (PEEK) with liquid crystalline poly(aryl ether ketone) containing substituted 3‐trifluoromethylbenzene side group (F‐PAEK), prepared by solution precipitation, have been investigated by rheometer. Dynamic rheological behaviors of the blends under the oscillatory shear mode are strongly dependent on blend composition. For PEEK‐rich blends, the systems show flow curves similar to those of the pure PEEK, i.e., dynamic storage modulus G′ is larger than dynamic loss modulus G″, showing the feature of elastic fluid. For F‐PAEK‐rich systems, the rheological behavior of the blends has a resemblance to pure F‐PAEK, i.e., G″ is greater than G′, showing the characteristic of viscous fluid. When the PEEK content is in the range of 50–70%, the blends exhibit an unusual rheological behavior, which is the result of phase inversion between the two components. Moreover, as a whole, the complex viscosity values of the blends are between those of two pure polymers and decrease with increasing F‐PAEK content. However, at 50% weight fraction of PEEK, the viscosity‐composition curves exhibit a local maximum, which may be mainly attributed to the phase separation of two components at such a composition. The changes of G′ and G″ with composition show a trend similar to that of complex viscosity. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4040–4044, 2006     

Bio-degradable vegetable oil based hyperbranched poly(ester amide) as an advanced surface coating material

Vegetable oil based hyperbranched poly(ester amide) (HBPEA) has enormous importance because of its unique characteristics. Thus the synthesis of HBPEA using N,N′-bis(2-hydroxy ethyl) castor oil fatty amide, maleic anhydride, phthalic anhydride and isophthalic acid as A₂ monomers and diethanol amine, as B₃ monomer was reported for the first time. The chemical structure of the synthesized resin was characterized by Fourier transform infrared (FTIR) and nuclear magnetic resonance (¹H NMR and ¹³C NMR) spectroscopic techniques. The degree of branching (DB) (as vouched by ¹H NMR analysis) and initial degradation temperature were found to increase with the increment in B₃ monomer content. Resins with 5 and 10 wt% of B₃ monomer showed shear thinning behavior while rheopectic nature of HBPEA with 15 wt% of B₃ content was observed. The evaluation of tensile strength, elongation at break, abrasion resistance, adhesion strength, scratch hardness, gloss, impact strength and chemical resistance complemented by microbial and lipolytic degradation forward the epoxy cured thermosets as advanced biodegradable surface coating materials.     

Strengthening of poly(butylene adipate-co-terephthalate) by melt blending with a liquid crystalline polymer

Poly(butylene adipate-co-terephthalate) (PBAT) is a soft biodegradable polymer with a low melting temperature. PBAT has been melt-blended with a liquid crystalline polymer (LCP) aiming at preparing a new biodegradable polymer blend with improved mechanical properties. The phase structure and crystalline morphologies of the PBAT/LCP blends were investigated using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), and transmission electron microscopy (TEM). It was found that the LCP domains are precisely dispersed in the PBAT matrix and that these domains act as the nuclei for PBAT crystallization. The nonisothermal crystallization temperature from the melt was dramatically shifted from 50°C to about 95°C by the addition of 20% LCP. In addition, the tensile modulus of the prepared blends increases gradually with increasing LCP content, indicating the excellent strengthening effects of LCP on the PBAT matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis,characterization and properties of a castor oil modified biodegradable poly(ester amide) resin

A biodegradable poly(ester amide) resin was synthesized from N,N-bis(2-hydroxy ethyl) fatty amide of castor oil with maleic anhydride, phthalic anhydride and isophthalic acid (100:30:35:35 mole ratio) by the polycondensation process. The fatty amide of the oil was obtained for the first time with 95% yield. The chemical structure of the synthesized resin was characterized by spectroscopic techniques like FTIR, ¹H NMR and ¹³C NMR. Various physical properties such as acid value, saponification value, iodine value, specific gravity and viscosity of the resin were also determined. Further the rheological behavior, studied in the steady shear mode showed shear thinning behavior of the resin. The epoxy cured poly(ester amide) thermoset using poly(amido amine) hardener exhibited better properties than with the cycloaliphatic amine hardener cured system. TGA studies also revealed higher thermal stability of the former system than the latter. In vitro-biodegradation study of the poly(ester amide) thermoset using Pseudomonas aeruginosa and Bacillus subtilus bacteria revealed superior biodegradability of the thermoset using the former bacterial strain. Excellent chemical resistance against various chemical media including alkali was observed for epoxy-poly(amido amine) cured poly(ester amide) resin over epoxy-cycloaliphatic amine one. The epoxy-poly(amido amine) cured poly(ester amide) thermoset thus has the potential to be used as surface coating material.