Copolyesters of glycols and bisphenols: A new preparative process

A new process for the preparation of copolyesters of glycols and bisphenols is described. Employing a preformed polyester, an acid, and a bisphenol diacetate, the procedure is useful for a variety of copolyesters. It is illustrated with the preparation of copolyterephthalates of ethylene glycol and 4,4′-isopropylidenediphenol. The reaction is proposed to proceed by an initial cleavage of the polyester, followed by polymerization of the acid- and acetate-terminated products. Intermediate heterogeneous structures then equilibrate.     

Direct polyesterification promoted by a complex of diphenyl chlorophosphate with LiBr

The diphenyl chlorophosphate (DPCP)-promoted polycondensation reaction between aromatic dicarboxylic acids and bisphenols was largely improved by carrying out the reaction in the presence of lithium halides to give high molecular weight aromatic polyesters. Among the halides LiBr, which is capable of forming a complex with hexamethylphosphoramide, was most effective, suggesting that a similar complexation of DPCP with LiBr in pyridine facilitates the complete reaction of DPCP with carboxyl groups. The complex could selectively activate carboxyl groups of hydroxybenzoic acids to give high molecular weight copolyesters from several combinations of aromatic hydroxy acids. The reaction could also be adaptable to the copolycondensations of a mixture of the dicarboxylic acids, bisphenols, and hydroxybenzoic acids.     

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.     

Direct polycondensations of hydroxybenzoic acids by use of diphenyl chlorophosphate in the presence of N,N-dimethylformamide

Direct polycondensation reaction of hydroxybenzoic acids with diphenyl chlorophosphate (DPCP) in pyridine was largely improved by carrying out the reaction in the presence of a formamide. Among the formamides examined, N,N-dimethylformamide (DMF), N,N-dimethylformamide, and N,N-dimethylacetamide were favorably used. A Vilsmeier adduct thus derived from DPCP and DMF was very effective especially for the preparation of high-molecularweight copolyesters from hydroxybenzoic acids. Copolymers of several combinations of hydroxybenzoic acids were prepared and their solubility and thermal properties were investigated. The polycondensations of aromatic dicarboxylic acids and bisphenols with the adduct were also studied.     

Preparation of aromatic copolyesteramides by the direct polycondensation with a vilsmeier adduct derived from tosyl chloride and N,N-dimethylformamide

The reaction promoted by Vilsmeier adduct derived from tosyl chloride (TsCl) with N,N-dimethylformamide (DMF) was successfully applied to the preparation of copolyesteramides of high molecular weights directly from aromatic dicarboxylic acids, diamines, and bisphenols. The polycondensation was significantly affected by the reaction of activated dicarboxylic acids with bisphenols and diamines. Addition of a mixture of bisphenols and diamines likely caused gelation of the reaction mixtures, resulting in insoluble polymers, especially with high mol % diamines. Stepweise addition of them, however, gave the homogeneous reaction mixtures and copolymers of better solubility. These phenomena were studied in terms of sequence length distribution of polyester units, which was estimated by thermal analyses of the random copolymers prepared under various conditions for the initial reaction with bisphenols.     

Preparation of copolyesters from diols and bisphenols by the solution polycondensation with TsCl/DMF/Py as a condensing agent

A novel synthetic method for the preparation of copolyesters comprised of diols and bisphenols using tosyl chloride (TsCl)/DMF/pyridine (Py) as a condensing agent has been developed. A variety of combinations of monomers could produce relatively high molecular weight copolymers, and better results were obtained by initial oligomerization of diols followed by bisphenols. In order to demonstrate usefulness of this method, copolymers comprised of IPA/TPA (50/50), bis(2‐hydroxyethyl)terephthalate (BHET),and several bisphenols were prepared and compared to the poly(ethylene terephthalate) (PET) modified by TPA and 2,2‐bis(4‐hydroxyphenyl)propane (BPA) diacetate in terms of their thermal properties. The length of mesogenic unit segments in the thermotropic IPA/TPA (50/50)‐BHET/ 4,4′‐dihydroxybenzophenone (4,4′‐DHBP) (50/50) copolymer was changed by initial reaction of BHET followed by dropwise addition of 4,4′‐DHBP in the two‐stage polycondensation and also by varying the amounts of BHET used at the initial and final stages in the three‐stage copolycondensation, and the results were studied by NMR and their thermal properties. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1270–1276, 2000     

Aliphatic–aromatic copolyesters derived from 2,2,4,4‐tetramethyl‐1,3‐cyclobutanediol

With the massive changes taking place in the world today, the development of new thermally and mechanically stable polymeric materials is of utmost importance. This article focuses on the synthesis and thermal characterization of a new series of copolyesters that incorporate both aromatic as well as aliphatic diols. This is of interest because most polymer materials that exhibit high thermal and/or mechanical properties contain aromatic monomer units only. These aromatic units usually contribute to either the thermal or mechanical properties but typically not both. An example of this is bisphenol A polycarbonate, which has high mechanical properties but only moderate thermal properties when compared, for example, to polyimides. In recent years there has been an interest in copolyesters that contain 2,2,4,4‐tetramethyl‐1,3‐cyclobutanediol (CBDO). This aliphatic monomer imparts some very unique thermal as well as mechanical properties. This article will report the thermal properties of a new series of CBDO‐based copolyesters. These polymers include CBDO, a series of bisphenols, and terephthaloyl chloride. The series of bisphenols discussed here include bisphenol A, AF, F, and HPF. These polymers display glass transition temperatures near 200 °C and decomposition temperatures from 390–420 °C (Argon) and from 385–410 °C (Air). © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3473–3478, 2004     

Aromatic-aliphatic copolyesters—II. Various polycondensation processes

Aromatic aliphatic copolyesters, using hydroquinone, resorcinol, 4,4′-dihydroxybiphenyl (DHBP) 2,2 bis(4-hydroxyphenyl)propane and 4,4′-dihydroxydiphenyl sulphone (DHDPS) as bisphenols and ethylene glycol as diol, have been synthesized by interfacial, low temperature and high temperature solution condensation. Relative reactivities of these bisphenols and ethylene glycol have been evaluated by various polycondensation methods at a fixed ratio of bisphenol/glycol. Decrease in the extent of polymerization and viscosity was observed by incorporation of aliphatic diol. Viscosity was also influenced by the chemical structure of the bisphenol.     

Unsaturated polyamides and polyesters prepared from 1,4-bis(2-carboxyvinyl)benzene and 4-hydroxycinnamic acid

Various unsaturated polyamides and polyesters were prepared from the reactions of 1,4-bis(2-carboxyvinyl)benzene acid chloride with aromatic diamines and bisphenols, respectively. In addition, various unsaturated homo- and copolyesters were synthesized from 4-hydroxycinnamic acid and 4-hydroxybenzoic acid. They were heat-cured to thermally stable resins. The polymers were characterized by inherent viscosity measurements, FT-IR, x-ray, DTA, TMA, TGA, and isothermal gravimetric analysis. The water absorption as well as the solubility behavior of the polymers was also investigated. © 1996 John Wiley & Sons, Inc.     

超高效液相色谱-串联质谱法同时测定塑料包装矿泉水中11种双酚类化合物

建立了同时测定塑料包装矿泉水中11种双酚类化合物的超高效液相色谱-串联质谱（UPLC-MS/MS）分析方法。以真空冷冻干燥的方法对样品进行前处理。使用Waters ACQUITY UPLC BEH C₁₈色谱柱（100 mm×2.1 mm,1.7 μm）进行分离,以甲醇和0.1%（v/v）氨水为流动相对目标物进行梯度洗脱。在电喷雾负离子模式及多反应监测（MRM）模式下进行定性和定量分析。结果表明,11种双酚类化合物在线性范围内线性关系良好,线性相关系数（R²）均大于0.997;目标物的检出限为0.01~1.00 μg/L;3个加标水平下的回收率为75.3%~102.1%,相对标准偏差为1.5%~8.9%。本方法准确、简便、快速,可用于塑料包装矿泉水中双酚类化合物的实际检测。     

Direct polycondensation with tosyl chloride in pyridine by formamide catalyzed alcoholysis

The reaction with tosyl chloride was significantly promoted by controlling alcoholysis with bisphenols in the presence of catalytic amounts of formamides to give aromatic polyesters with high molecular weights from aromatic dicarboxylic acids and bisphenols. Mechanistic features of the reaction were studied by use of various formamides and other arylsulfonyl chlorides, as well as by varying the addition mode of bisphenols and changing the relative amount of formamide. The reaction was successfully applied to the preparation of aromatic polyesteramides with high molecular weights from aromatic dicarboxylic acids, bisphenols, and diamines, but with limited success to that of polyamides.     

Synthesis of hydrolytically degradable aromatic polyesters with lactide moieties

A synthetic route to higher molecular weight processable polyesters with bisphenol A terephthalate/isophthalate moieties and lactide moieties which are of potential interest for tissue engineering is described. The combination of aliphatic and aromatic moieties is a promising concept for processable polyesters with potential sites for physiological degradation and improved mechanical properties. The molecular structure of the copolyesters prepared by melt condensation via an acid chloride route and incorporation of the lactide moieties by transesterification of an oligo dl -lactide was confirmed by infrared, ¹H and ¹³C nuclear magnetic resonance spectroscopy as well as gel permeation chromatography. The thermal and mechanical properties of copolyesters with different amounts of lactide moieties are reported and correlated with their composition. The reaction mechanism by transesterification was proved by a model reaction with a physical blend of the components and the hydrolytical behavior of the copolyesters under physiological conditions has been investigated. © 1997 John Wiley & Sons, Ltd.     

Novel copolyesters containing naphthalene structure. II. Copolyesters prepared from 2,6-dimethyl naphthalate, 1,4-dimethyl terephthalate,and ethylene glycol

Copolyesters containing rigid segments (naphthalene and terephthalene) and flexible seg-ments (aliphatic diol) structure were synthesized from DMN/DMT/EG (2,6-dimethyl naphthalate/1,4-dimethyl terephthalate/ethylene glycol) ternary monomers with various mole ratios. Copolyesters having intrinsic viscosities of 0.52–0.65 dL/g were obtained by melt polycondensation in the presence of metallic catalysts. The effect of reaction tem-perature and time on the formation of the copolyesters was investigated to obtain an op-timum condition for copolyester manufacturing. The optimum condition for PNT (poly-ethylene naphthalate terephthalate) copolyester manufacturing is the transesterification under nitrogen atmosphere for 4 h at a temperature of 185±2°C followed by polymerization under 2 mm Hg for 2 h at a temperature of 280°C. Most copolyesters have better solubilities than poly(ethylene naphthalate) (PEN) and poly(ethylene terephthalate) (PET) in various solvents. The effect of the starting mole ratio of DMN, DMT, and EG on the thermal properties of the resulted copolyesters was also investigated using differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). Glass transition temperatures of copolyesters were in the range of 70.7–115.2°C, and 10% weight loss in nitrogen were all above 426°C. © 1995 John Wiley & Sons, Inc.     

Direct polyesterification with thionyl chloride in pyridine improved by a modification of monomer sequences in copolymers

The direct polyesterification with thionyl chloride (SOCl₂) in pyridine was further investigated. Copolycondensations of dicarboxylic acids, bisphenols, and hydroxybenzoic acids were significantly affected by the reaction temperatures and combinations of monomers which could change relative rates of alcoholyses of the activated dicarboxylic acids and the hydroxyacids consequently to vary monomer sequences in the copolymers resulted. The sequences were tried to be varied more directly by stepwise reactions of monomers in copolycondensations of dicarboxylic acids, bisphenols, and p-hydroxybenzoic acid (PHB), as well as PHB and m-hydroxybenzoic acid (MHB). The reactions proceeded smoothly and satisfactorily when carried out by initial reaction of dicarboxylic acids and PHB followed by bisphenols likely to favor sequential to random distributions of monomers. Reverse addition of PHB and bisphenols, and then dicarboxylic acids resulted in rapid precipitation due to some oligomerization of PHB at an earlier stage of reaction, and largely retarded the reaction. This was also the case for the copolycondensation of PHB and MHB. Copolymers of high inherent viscosities with up to 65 mol% PHB could be obtained by initial reaction of MHB followed by PHB.     

Synthesis and properties of poly(arylene ether imide ketone)s

Poly(arylene ether ketone)s containing imide units were prepared by the aromatic nucleophilic displacement reaction of the potassium salts of bisphenols with bis(4-fluorobenzoyl)phthalimides in N-methyl-2-pyrrolidone at elevated temperature. The polymers having inherent viscosities of 0.34–0.77 dL/g were obtained in 2 h. The polymers exhibited glass transition temperatures ranging from 216 to 268°C and decomposition temperatures (5% weight loss under air atmosphere) ranging from 450–570°C mainly depending on the bisphenols used in the polymer synthesis. The isothermal TGA measurements (400°C under air or nitrogen atmosphere) revealed that the 4,4'-biphenol- and hydroquinone-based poly(arylene ether ketone imide)s belong to a superior class of heat resistant polymers. The mechanical properties of these polymers are also described. © 1994 John Wiley & Sons, Inc.     

Copoly(amide—ester)s from p-aminobenzoic and hydroxybenzoic acids by the direct polycondensation with diphenyl chlorophosphate and LiCl

The reaction promoted by diphenyl chlorophosphate (DPCP) and LiCl was found to be effectively used for the preparation of aromatic polyesters with high molecular weights directly from hydroxybenzoic acids when the condensing agent was added dropwise. The reaction was successfully to the direct polycondensation reaction of p-aminobenzoic and hydroxybenzoic acids, giving high-molecular-weight copoly(amide—ester)s soluble in amide or phenolic solvents. Copolycondensations of isophthalic and terephthalic acids with bisphenols and aromatic diamines were also examined by adding the DPCP solution to a mixture of these monomers or by initial reaction of DPCP with the acids followed by dropwise addition of a mixture of bisphenols and the diamines. The latter stepwise reaction gave random copolymers soluble in amide and phenolic solvents. Thermal properties of these copolymers were studied.     

Direct polyesterification with thionyl chloride in pyridine improved by a modification of monomer sequences in copolymers

The direct polyesterification with thionyl chloride (SOCl₂) in pyridine was further investigated. Copolycondensations of dicarboxylic acids, bisphenols, and hydroxybenzoic acids were significantly affected by the reaction temperatures and combinations of monomers which could change relative rates of alcoholyses of the activated dicarboxylic acids and the hydroxyacids consequently to vary monomer sequences in the copolymers resulted. The sequences were tried to be varied more directly by stepwise reactions of monomers in copolycondensations of dicarboxylic acids, bisphenols, and p-hydroxybenzoic acid (PHB), as well as PHB and m-hydroxybenzoic acid (MHB). The reactions proceeded smoothly and satisfactorily when carried out by initial reaction of dicarboxylic acids and PHB followed by bisphenols likely to favor sequential to random distributions of monomers. Reverse addition of PHB and bisphenols, and then dicarboxylic acids resulted in rapid precipitation due to some oligomerization of PHB at an earlier stage of reaction, and largely retarded the reaction. This was also the case for the copolycondensation of PHB and MHB. Copolymers of high inherent viscosities with up to 65 mol % PHB could be obtained by initial reaction of MHB followed by PHB.     

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.     

Preparation of polyaryl esters by a new direct polycondensation reaction with arylsulfonyl chlorides in pyridine

Arylsulfonyl chlorides were successfully used as a new condensing agent for the synthesis of polyaryl esters by the direct polycondensation of aromatic dicarboxylic acids and bisphenols. High-molecular-weight polymers (M_w = 84,000) were prepared by reacting dicarboxylic acids with the sulfonyl chlorides in pyridine in the presence of LiCI, followed by treating with a pyridine solution of bisphenols. The polycondensation was significantly affected by factors, such as, the kind of arylsulfonyl chlorides, its amount, the conditions of initial reaction of the acids with the sulfonyl chlorides, the amounts of LiCI added, and dropwise addition of bisphenols.     

Preparation and Characterization of Biobased Lignin-Co-Polyester/Amide Thermoplastics

More than 23 million tonnes of lignin are produced annually in the US from wood pulping and 98% of this lignin is burnt. Therefore, creating products from lignin, such as plastics, offers an approach for obtaining sustainable materials in a circular economy. Lignin-based copolymers were synthesized using a single pot, solvent free, melt condensation reaction. The synthesis occurred in two stages. In the first stage, a biobased prepolymer consisting of butanediol (BD, 0.8–1 molar content) and a diacid (succinic (SA), adipic (AA) and suberic acids (SuA), with varying amounts of diaminobutane (DAB, 0–0.2 molar content) was heated under vacuum and monitored by Fourier transform infra-red (FTIR) spectroscopy and electrospray ionization-mass spectrometry (ESI-MS). In the second stage, prepolymer was mixed with a softwood kraft lignin (0–50 wt.%) and further reacted under vacuum at elevated temperature. Progression of the polymerization reaction was monitored using FTIR spectroscopy. The lignin-copolyester/amide properties were characterized using tensile testing, X-ray diffraction (XRD), dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) techniques. Lignin co-polymer tensile (strength 0.1–2.1 MPa and modulus 2 to 338 MPa) properties were found to be influenced by the diacid chain length, lignin, and DAB contents. The lignin-copolymers were shown to be semi-crystalline polymer and have thermoplastic behavior. The SA based copolyesters/amides were relatively stiff and brittle materials while the AA based copolyesters/amides were flexible and the SuA based copolyesters/amides fell in-between. Additionally, > 30 wt.% lignin the lignin- copolyesters/amides did not exhibit melt behavior. Lignin-co-polyester/amides can be generated using green synthesis methods from biobased building blocks. The lignin- copolyesters/amides properties could be tuned based on the lignin content, DAB content and diacid chain length. This approach shows that undervalued lignin can be used in as a macromonomer in producing thermoplastic materials.