含T-型和棒型两种液晶基元的主链型液晶共聚酯的合成和表征

以４，４′（α，ω 癸二酰氧）二苯甲酰氯，２ （４′ 乙氧基苯基）对苯二酚和联苯酚为单体，通过溶液缩聚反应，合成了一系列含Ｔ 型和棒型两种液晶基元的主链型芳族共聚酯．采用ＤＳＣ、偏光显微镜和Ｘ 射线衍射方法研究了共聚物的液晶行为，发现所有聚合物均有很好的热致液晶性且随聚合物中联苯酚用量的改变，共聚物的熔点（Ｔｍ）和液晶态清亮点（Ｔｉ）呈规律性变化．     

PROPERTIES AND MICROSTRUCTURE OF AROMATIC LIQUID CRYSTALLINE COPOLYESTERS

The properties and structures of thermotropical liquid crystalline copolyesters basedon p-hydroxybenzoic acid (PHBA), terephthalic acid (TPA) and bisphenol A (BPA) werestudied by DSC, WAXD, hot stage polarized microscopy and NMR. It was found that mostof the copolyesters were soluble in many common organic solvents. The copolyesters hadfow T_m/T_f values and a broad range of liquid crystal phase, making the polymers readilymelt-processable. The effects of annealing at different temperatures on the copolyestercontaining 33% PHBA were also discussed. It was noted that annealing at ca. 200℃(below Tc - n) could lead to the increasing of the crystallinity of the copolyester while themicrostructure and sequence structure had not changed. Annealing at ca.280℃ (nearTc - n) could bring a change of crystal and sequence structure and simultaneously madethe ndcrodomains be ordered more perfectly.     

含X-型二维液晶基元和冠醚环的液晶共聚酯的研究

合成了一系列新的含X-型二维液晶基元和反式-4,4'-双(4-羟基苯基偶氮)二苯并-14-冠-4冠醚环的主链型液晶共聚酯. 通过GPC, [η], DSC, TG, WAXD和POM对其液晶性研究发现, 所有的共聚酯都呈现出向列相的丝状织构或纹影织构. 共聚酯的熔融温度(T_m)和各向同性温度(T_i)随共聚酯分子中反式-4,4'-双(4-羟基苯基偶氮)二苯并-14-冠-4用量的改变呈规律性变化.     

Study on poly(oxybenzoate-p-trimethylene terephthalate) copolymer

This study examined copolymers synthesized from poly(trimethylene terephthalate) (PTT) and p-acetoxybenzoic acid using solution proton nuclear magnetic resonance (NMR) spectroscopy. Proton NMR spectra showed that these p-oxybenzoate (POB)/PTT copolyesters were almost random copolymers because the preference factor of POB bonded to another POB unit in these copolyesters is close to 1.0 with a POB content between 20 and 80 mol%.The melting and crystallization behaviors of these copolyesters were studied by differential scanning calorimetry (DSC). In the heating DSC scan of the POB rich composition, the endothermic peak is weaker because the enthalpy of fusion decreased due to a melting transition from a crystalline to anisotropy liquid state. Thermogravimetric analysis results indicated that the decomposition temperature (T_d) increased with POB content. The crystalline morphology of the copolyester was further investigated with a polarized optical microscope, indicating that the POB/PTT copolyesters with 60 mol% POB are highly anisotropic in the liquid state.     

Syntheses and Physical Characterization of Biodegradable Poly(butylene succinate-co-butylene itaconate) Copolymers

Biodegradable aliphatic poly (butylene succinate-co-butylene itaconate) (PBSBIs) from succinic acid, itaconic acid and 1,4-butanediol were synthesized through a polycondensation with titanium tetraisoproxide (TTP), diphenylphosphinic acid (DPPA) as the novel co-catalysts in this article. By means of gel permeation chromatography (GPC) and nuclear magnetic resonance spectrometer (NMR), it was revealed that the PBSI copolyesters had number average molecular weights M_n higher than 3.0 × 10⁴, and the composition of copolyesters was in good agreement with that expected from the feed composition of the reactants. With respect to thermal properties, melting temperature (T_m), crystallization temperature (T_c), and crystallinity (X_c) were found to decrease with increasing the BI/BS unit molar ratio up to 0.67. X-ray diffraction patterns indicated that the PBSIs copolyesters had the same crystal structure as the PBS. While increasing the BI/BS unit molar ratio up to 1, the copolyesters would change into insolubility and inmelt crosslinked elastomer. Otherwise, the observation of polarizing optical microscope (POM) showed that the spherulite size of copolyesters gradually became smaller with the increasing of BI unit content. Experimental results also showed that the contents of itaconic acid had an important effect on the biodegradable performance of copolyesters.     

Thermotropic copolyesters having ordered comonomer sequences and flexible spacers

A series of new copolyesters having ordered comonomer sequences were synthesized via multistep routes and their properties such as glass transition (T_g) and melting temperatures (T_m), crystallization tendency, and mesomorphic properties were compared with those of the corresponding random copolyesters. All of the present copolyesters contain 1,8-octamethylene or 1,10-decamethylene spacers and hydroquinone (HQ) and terephthalic acid (TPA) moieties. In general, both melting and clearing temperatures of the ordered sequence copolyesters were much higher than those of the random counterparts. Crystallization tendency, however, was comparable. All of the present copolyesters are thermotropic and form nematic phase in melts. © 1993 John Wiley & Sons, Inc.     

Investigations on aromatic polyesters with polynaphthalene systems in the main chain—IX. Influence of the chain structure of aromatic copolyesters on their glass transition temperatures

Glass transition temperatures of terephthalic copolyesters of 4,4′dihydroxydinaphthyl 1,1′ and 2,2 bis(4-hydroxyphenyl)propane with various mole ratios of the comonomers and different chain structures have been measured. A relationship has been found between T_g and the chain structure of aromatic copolyesters with polynaphthalene rings in the chain.     

Novel copolyesters containing naphthalene structure. I. From bis(hydroxyalkyl)naphthalate and bis[4-(2-hydroxyethoxy)aryl] compounds

Copolyesters containing naphthalene structure were synthesized from bis(hydroxyethyl)naphthalate (BHEN) or bis(hydroxybutyl)naphthalate (BHBN) and various aralkyloxy diols. The starting bis[4-(2-hydroxyethoxy)aryl] compounds were derived from a nucleophilic substitution of various bisphenols with ethylene carbonate in the presence of KI. Copolyesters having intrinsic viscosities of 0.45–0.60 dL/g were obtained by the melt polycondensation in the presence of metallic catalysts. The effect of reaction temperature and time on the formation of copolyesters were investigated to obtain an optimum condition for copolyesters manufacturing. Most copolyesters have better solubilities than polyethylene naphthalate (PEN) or polybutylene naphthalate (PBN) in aprotic solvents, such as N-methyl-2-pyrrolidone or m-cresol. The thermal properties of the copolyesters were investigated by the differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). Glass transition temperatures (T_g) of copolyesters result from BHEN were in the range of 90–141°C, and 10% weight loss in nitrogen were all above 460°C. Another series of copolyesters result from BHBN have T_g in the range of 75–135°C, and 10% weight loss in nitrogen of over 420°C. © 1996 John Wiley & Sons, Inc.     

含X-型二维液晶基元和顺式-4,4′-双(4-羟基苯基偶氮)二苯并-14-冠-4冠醚环液晶共聚酯的合成与表征

以4,4′-(α,ω-辛二酰氧)二苯甲酰氯(M1)、2,5-二(对十二烷氧基苯甲酰氧基)对苯二酚(M2)和顺式-4,4′-双(4-羟基苯基偶氮)二苯并-14-冠-4(M3)为单体,通过溶液共缩聚反应,合成了一系列含X-型二维液晶基元和顺式-4,4′-双(4-羟基苯基偶氮)二苯并-14-冠-4冠醚环的主链型液晶共聚酯.单体1(M1)由对羟基苯甲酸和辛二酰氯,通过酯化和取代反应制备,单体2(M2)由2,5-二羟基苯醌和对十二烷氧基苯甲酰氯通过酯化和还原反应制备,单体3(M3)由顺式-二氨基二苯并-14-冠-4和苯酚通过重氮化和偶联反应制备.共聚酯的分子量不高,[η]在0·35~0·25dL/g之间.单体的化学结构通过IR、UV、1H-NMR、MS和元素分析等方法确证.共聚酯的外观为黄色粉状固体,除CP9外,室温下不溶于CHCl3和THF溶剂.共聚酯的性质采用GPC、[η]、DSC、TG、WAXD和POM等方法进行了研究.发现所有的共聚酯加热到各自的熔融温度以上都能形成液晶态,在液晶态可以观察到向列相的丝状织构或纹影织构.共聚酯的熔融温度(Tm)和各向同性温度(Ti)随共聚酯分子中顺式-4,4′-双(4-羟基苯基偶氮)二苯并-14-冠-4用量的改变呈规律性变化.WAXD研究进一步证实了共聚酯的液晶性.     

Synthesis and structure of biodegradable hexylene terephthalate-co-lactide copolyesters

To obtain a biodegradable polymer material with satisfactory thermal properties, higher elongation and modulus of elasticity, a new copolyester, poly(hexylene terephthalate-co-lactide) (PHTL), was synthesized via direct polycondensation from terephthaloyl dichloride, 1,6-hexanediol and oligo(lactic acid). The resulting copolyesters were characterized by proton nuclear magnetic resonance (¹H NMR), differential scanning calorimetry (DSC), thermogravimetry (TG) and wide-angle X-ray scattering (WAXS). By using the relative integral areas of the dyad peaks in ¹H NMR spectrum of copolyesters PHTL, the sequence lengths of the hexylene terephthalate and lactide units in the resultant copolyesters are 3.5 and 1.5, respectively. Compared to poly(hexylene terephthalate) (PHT), PHTL has lower T _m but higher T _g due to the incorporation of lactide unit into the main chains of copolyesters. The degradation test of copolyesters under a physiological condition shows that the degradability of PHTL is sped up due to incorporation of lactide segments.     

Fully aromatic thermotropic liquid crystalline polyesters of 3-phenyl-4,4′-biphenol with 4,4′-benzophenone dicarboxylic acid

A series of fully aromatic, thermotropic polyesters, derived from 3-phenyl-4,4′-biphenol (MPBP), nonlinear 4,4′-benzophenone dicarboxylic acid (4,4′-BDA), and various other comonomers was prepared by the melt polycondensation method and characterized for their thermotropic liquid crystalline behavior by a variety of experimental techniques. The homopolymer of MPBP with 4,4′-BDA had a fusion temperature (T_f) at 240°C, exhibited a nematic liquid crystalline phase, and had a narrow liquid crystalline range of 60°C. All of the copolyesters of MPBP with 4,4′-BDA and either 30 mol % 4-hydroxybenzoic acid (HBA), 6-hydroxy-2-naphthoic acid (HNA) or 50 mol % terephthalic acid (TA), 2,6-naphthale-nedicarboxylic acid (2,6-NDA) and low T_f values in the range of 210–230°C, exhibited a nematic phase, and had accessible isotropization transitions (T_i) in the range of 320–420°C, respectively. As expected, each of them had a broader range of liquid crystalline phase than the homopolymer. They had a “frozen” nematic, glassy order as determined with the wide-angle X-ray diffraction (WAXD) studies. The morphology of each of the “as-made” polyesters had a fibrous structure as determined with the scanning electron microscopy (SEM), which arises because of the liquid crystalline domains. Moreover, they had higher glass transition temperatures (T_g) in the range of 167–190°C than those of other liquid crystalline polyesters, and excellent thermal stabilities (T_d) in the range of 500–533°C, respectively. © 1995 John Wiley & Sons, Inc.     

新型手性近晶C相液晶共聚酯的设计与合成

以对苯二甲酰氯 ,2 ,5 二 [4 ((s) 2 甲基丁氧基 )苯甲酰氧基 ]对苯二酚和乙二醇、一缩乙二醇、二缩三乙二醇、三缩四乙二醇和聚乙二醇为单体 ,采用低温溶液缩聚方法 ,合成了一系列新的手性近晶C相串型液晶共聚酯 .共聚酯通过GPC、DSC、TG、WAXD、偏光显微镜和旋光仪等方法表征 .发现所有的共聚酯加热至各自的熔点以上都能形成液晶态 ,在液晶态可以观察到近晶相的焦锥织构 ,所有的手性化合物和共聚酯都有较高的旋光性 .通过变温X 射线衍射研究结合偏光显微镜观察和旋光分析证明它们为手性近晶C相 .所有共聚酯的熔融温度 (Tm)和各向同性温度 (Ti)随共聚酯中不同柔性链段长度的增加逐渐降低 ,液晶态温度范围变宽     

含X-型二维液晶基元和反式-4,4′-双(4-羟基苯基偶氮)二苯并-18-冠-6冠醚环的液晶共聚酯的合成与表征

以4,4-′(α,ω己二酰氧)二苯甲酰氯(M1)、2,5-二(对辛氧基苯甲酰氧基)氢醌(M2)和反式4,4′-双(4羟基苯基偶氮)二苯并18冠6(M3)为单体,通过溶液共缩聚反应,合成了一系列含X型二维液晶基元和反式4,4′双(4羟基苯基偶氮)二苯并18冠6冠醚环的主链型液晶共聚酯.共聚酯的分子量不高,[η]在0.37～0.25dL g之间.单体的化学结构通过IR、UV、H NMR、MS和元素分析等方法确证.共聚酯的外观为黄色粉状固体,除CP9外,室温下不溶于CHCl3和THF溶剂.共聚酯的性质采用GPC、[η]、DSC、TG、WAXD和POM等方法进行了研究.发现所有的共聚酯加热到各自的熔融温度以上都能形成液晶态,在液晶态可以观察到近晶相的镶嵌织构或焦锥织构或破扇型织构和向列相的球粒织构或丝状织构或纹影织构.共聚酯的熔融温度(Tm)和各向同性温度(Ti)随共聚酯分子中反式4,4′双(4-羟基苯基偶氮)二苯并18冠6用量的改变呈规律性变化.WAXD研究进一步证实了共聚酯的液晶性.     

Effect of Polycondensation Reaction Conditions on the Properties of Thermotropic Liquid‐Crystalline Copolyester

In this study a range of wholly aromatic copolyesters based on kink m‐acetoxybenzoic acid (m‐ABA) monomer (33 mol%) and equimolar‐linear p‐acetoxybenzoic acid (p‐ABA), hydroquinone diacetate (HQDA) and terephthalic acid (TPA) monomers (67 mol%) have been synthesized by melt polycondensation reaction process at 280°C and 260°C for different time intervals. Characterization of copolyesters were performed by solution viscosity measurement, wide–angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), hot‐stage polarized light microscopy, proton‐nuclear magnetic resonance analysis (¹H‐NMR). According to the results obtained, copolyesters showed thermotropic liquid crystalline behavior in an appropriate temperature range. The copolyesters were prepared in high yields. It was observed that the intrinsic viscosities of the copolyesters are increased regularly with increasing polymerization time and temperature. All the copolyesters were soluble in a trifluoroacetic acid/dichloromethane (30:70 v/v) except the copolyesters which were synthesized at 280°C in 5 h. According to the WAXD results; the degree of crystallinity of copolyesters were found to be between 5–15%. DSC and hot stage polarized light microscopy results showed that all the copolyesters are melt processable and a significant molecular interaction exist in a very broad temperature range (160°C and 165°C) in the nematic mesophase. The T_g values are increased with an increasing polycondensation reaction time and temperature and they were observed between 93–126°C. Fibers prepared by a hand‐spinning technique from the polymer melt exhibit well‐developed fibrillar structure parallel to the fiber axis.     

Synthesis,characterization, and in vitro degradation of thermotropic polyesters and copolyesters based on terephthalic acid, 3‐(4‐hydroxyphenyl)propionic acid,and glycols

A new series of thermotropic liquid‐crystalline (LC) polyesters were prepared from a diacyl chloride derivative of 4,4′‐(terephthaloyldioxy)‐di‐4‐phenylpropionic acid (PTP) and glycols with a different number of methylene groups (n) [HO(CH₂)_n OH, n = 6–10, 12] by high‐temperature solution polycondensation in diphenyl oxide. PTP6/10 and PTP6/hydroquinone (H) LC copolyesters were also prepared according to a similar procedure. The chemical structure, LC, phase‐transition behaviors, thermal stability, and solubility were characterized by elemental analysis, Fourier transform infrared spectroscopy, ¹H and ¹³C NMR spectra, differential scanning calorimetry (DSC), thermogravimetric analysis, and a polarizing light microscope. The melting and isotropization temperatures decreased in a zigzag manner as the number of n increased. All of the polyesters formed a nematic phase with the exception of PTP8. The temperature ranges of the mesophase (ΔT) were much wider for the polyesters with an odd number of n's than those with an even number. ΔT increased markedly for the PTP6/10 and PTP6/H copolyesters. The in vitro degradations of the polymers were ascertained by enzymatic hydrolysis and alkaline hydrolysis. The model compound, PTP dihexylester, was synthesized and found to be degraded into terephthalic acid, 3‐(4‐hydroxyphenyl)propionic acid, and 1‐hexanol by Rhizopus delemar lipase, but PTPn homopolyesters and PTP6/10 and PTP6/H copolyesters were resistant to Rhizopus delemar hydrolysis. They were degradable in a sodium hydroxide buffer solution of pH 12 at 60 °C, depending on the number of n's and the copolymer composition. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3043–3051, 2001     

Biodegradable liquid crystalline aromatic/aliphatic copolyesters. Part I: Synthesis, characterization, and hydrolytic degradation of poly(butylene succinate-co-butylene terephthaloyldioxy dibenzoates)

To increase the thermal and mechanical properties of the aliphatic polyester poly(butylene succinate) (PBS), a series of potentially biodegradable liquid crystalline aromatic/aliphatic random copolyesters were prepared by melt polycondensation of new mesogenic monomers dimethyl 4,4′-(terephthaloyldioxy) dibenzoate (MTB), dimethyl succinate, and 1,4-butanediol. The synthesized copolyesters were characterized by means of proton nuclear magnetic resonance spectroscopy (¹H NMR), gel permeation chromatography (GPC), viscosity measurements, differential scanning calorimetry (DSC), thermogravimetry (TG), X-ray diffraction (XRD), polarizing light microscopy (PLM) and mechanical property measurements. The MTB content was varied so that the effects of the mesogen content on the thermal and mechanical properties, degradable behaviours and mesophase were examined. It was found that introducing the rigid rod mesogens could increase the thermal stability and the mechanical properties, while it reduced the melting temperature (T_m), the crystallization temperature (T_c), the degree of relative crystallinity (X_c) and the hydrolytic degradation rate. Only the homopolyester poly(butylenes terephthaloyldioxy dibenzoates) was able to show the schlieren texture characteristic of nematics.     

Layer structures. VI. Chiral sanidic polyesters derived from 2,5-bis (dodecyloxy) terephthalic acids and 4,4′-dihydroxybiphenyl

Copolycondensations of (S,S)-2,5-bis(2-methylbutyloxy) terephthaloylchloride with 2,5-bis(dodecyloxy)terephthaloylchloride and with 4,4′-bistrimethylsiloxybiphenyl yielded a series of novel chiral thermotropic copolyesters. These polyesters were characterized by elemental analyses, inherent viscosities, ¹H-NMR spectroscopy, optical rotations, optical microscopy, DSC measurements, and WAXS powder patterns recorded with synchrotron radiation under variation of the temperature. All homo- and copolyesters formed a solid sanidic layer structure with melting temperatures (T_m) ≥ 200°C. A broad enantiotropic nematic or cholesteric phase is formed above T_m with isotropization temperatures (T_is) in the range of 275–325°C. Yet, the T_m of the chiral homopolyester is so high (378°C) that the melting process is immediately followed by rapid degradation. The cholesteric phases of the copolyesters displayed unusual mobile schlieren textures, but a stable Grandjean texture was never obtained. Cholesteric domains consisting of loose bundles of more or less helical main chains are discussed as supramolecular order responsible for the observed textures and their pronounced temperature dependence. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 947–957, 1997     

Thermotropic main chain liquid crystalline polyesters containing ferrocene and phosphate units: synthesis and characterization

A new series of liquid crystalline main chain copolyesters were prepared, having ferrocene in the mesogenic segment and a methyl phosphate group along with a methylene spacer. The even numbered methylene groups were varied from two to ten. Liquid crystalline behaviour was investigated on a hot stage optical polarized microscope. Thermal properties of the polymers were analysed by TGA and DSC, revealing that the polymers yield high char products, probably caused by the formation of phosphorus and iron oxides. The glass transition (T _g) temperatures of the polymers were found to be fairly low, the result of the incorporation of bulky phosphorus and ferrocene moieties in the chain. The phase behaviour was analysed and correlated with the structure of the polymers. The liquid crystalline textures of the polymers became more transparent with increasing spacer length. Energy minimized structures for the polymer repeating units reveal that both the ferrocene and phosphorus moieties produce more molecular entanglement, thus reducing the T _g and T _m of the polymers.     

SYNTHESIS OF MAIN CHAIN LIQUID CRYSTALLINE COPOLYESTERS WITH X-SHAPED TWO-DIMENSIONAL MESOGENIC UNIT AND CROWN ETHER CYCLE

A novel series of main chain liquid crystalline copolyesters with X-shaped two-dimensional mesogenic unit and crown ether cycle of cis-4,4′-bis(4-hydroxyphenylazo) dibenzo-18-crown-6 was prepared via solution condensation polymerization from 4,4′-(α,ω-hexanedioyloxy) dibenzoyl dichloride (M1), 2,5-bis(p-octyloxybenzoyloxy) hydro-quinone (M2) and cis-4,4′-bis(4-hydroxyphenylazo) dibenzo-18-crown-6 (M3). Monomer M1 was synthesized by esterification and substitution of adipoyl chloride with p-hydroxybenzoic acid, monomer M2 was synthesized by esterfication and reduction reaction of 2,5-dihydroxybenzoquinone and p-octanoxybenzoyl chloride and monomer M3 was synthesized by diazotization and coupling reaction of cis-diaminodibenzo-18-crown-6 with phenol. The molecular weights of copolyesters are not high,and the intrinsic viscosity [η] of copolyesters ranges from 0.25-0.35. The monomers' structures were identified by using elemental analysis, IR, UV, 1H-NMR, MS, etc. All the copolyesters are yellowish powders and insoluble in THF and CHCl3 at room temperature except CP9. The properties of copolyesters were investigated by using GPC, [η] , DSC, TG,WAXD and POM. It was found that all the copolyesters entered into liquid crystal phase when they were heated to above their melting temperature (Tm). The typical smectic and nematic phase texture can be observed on POM. Their mesophase transition temperature and thermal stability change regularly with varying the content of cis-4,4′-bis(4-hydroxyphenylazo)dibenzo-18-crown-6 unit in the copolyesters.     

SYNTHESIS OF LIQUID CRYSTALLINE COPOLYESTERS WITH T-SHAPED TWO-DIMENSIONAL MESOGENIC UNIT AND CROWN ETHER CYCLE

A novel series of liquid crystalline copolyesters with T-shaped two-dimensional mesogenic unit and crown ether cycle of cis-4,4′-bis(4-hydroxyphenylazo)dibenzo-18-crown-6 was prepared via solution condensation polymerization from 4,4′-(α,ω-hexanedioyloxy)dibenzoyl dichloride(M_1),2-(4′-ethoxyphenyl)hydroquinone(M_2)and cis-4,4′-bis(4- hydroxyphenylazo)dibenzo-18-crown-6(M_3).The molecular weights of copolyesters are not high,and the intrinsic viscosity [η]of copolyesters ranges from 0.29-0.43.The monomer...