Attempt to control monomer sequences in copolycondensations of IPA,TPA, BPA,and PHB

Copolycondensations of IPA, TPA, BPA, and PHB were studied to investigate how PHB, which can form mesogenic segments, should be incorporated into the amorphous IPA/TPA–BPA polyester to obtain the thermotropic copolyester, unlike other copolymerizations studied so far by randomly introducing nonmesogenic components into the liquid crystalline polyesters. Random and controlled copolycondensations were attempted to regulate the segment length of mesogenic PHB units by stepwise addition of BPA and PHB through the two- and three-stage reactions using TsCl/DMF/Py as a condensing agent. Thermotropic copolyesters with ca. 40 mol % PHB could be obtained by a three-stage reaction, despite that more than 70 mol % PHB is needed to prepare by usual random copolymerization with PHB. The segment length of the PHB unit was indirectly studied from IPA/TPA–BPA oligomer distribution at initial reaction by means of GPC and from the NMR analysis of the resulting copolymers. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2371–2377, 1999     

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     

低分子量芳香族热致液晶聚（对羟基苯甲酸－对苯二甲酸双酚A酯）的研究

借酯交换反应，以对羟基苯甲酸、对苯二甲酸和双酚Ａ为单体通过淤浆聚合制备出６个低分子量芳香族热致液晶样品，即ＰＨＢＡ／ＴＰＡ／ＢＰＡ共聚酯．由于此单体含量不同的共聚酯样品在适当的溶剂中有较好的溶解性，故能进行许多表征．根据实验结果还得到了表示转变温度一组成关系的相图，并进行了讨论．     

Liquid crystal polymers. I. Preparation and properties of p-hydroxybenzoic acid copolyesters

High molecular weight copolyesters were prepared by the acidolysis of poly(ethylene terephthalate) with p-acetoxybenzoic acid and polycondensation through the acetate and carboxyl groups. The mechanical properties of the injection-molded copolyesters containing 40–90 mole- % p-hydroxybenzoic acid (PHB) were highly anisotropic and dependent upon the PHB content, polyester molecular weight, injection-molding temperature, and specimen thickness. As the injection-molding temperature increased and the specimen thickness decreased, the tensile strength, stiffness, and Izod impact strength increased when measured along the direction of flow of the polymer melt, and the coefficient of thermal expansion was zero. In some compositions these properties were superior to those of commercial glass fiber reinforced polyesters. Maximum tensile strengths, flexural moduli, notched Izod impact strengths, and minimum melt viscosities were obtained with polyesters containing 60–70 mole-% PHB. Higher oxygen indicies (39-40) and heat deflection temperatures (150-220°C) were obtained with 80–90 mole-% PHB.     

Liquid crystal polymers. I. Preparation and properties of p-hydroxybenzoic acid copolyesters

High molecular weight copolyesters were prepared by the acidolysis of poly(ethylene terephthalate) with p-acetoxybenzoic acid and polycondensation through the acetate and carboxyl groups. The mechanical properties of the injection-molded copolyesters containing 40–90 mole-% p-hydroxybenzoic acid (PHB) were highly anisotropic and dependent upon the PHB content, polyester molecular weight, injection-molding temperature, and specimen thickness. As the injection-molding temperature increased and the specimen thickness decreased, the tensile strength, stiffness, and Izod impact strength increased when measured along the direction of flow of the polymer melt, and the coefficient of thermal expansion was zero. In some compositions these properties were superior to those of commercial glass fiber reinforced polyesters. Maximum tensile strengths, flexural moduli, notched Izod impact strengths, and minimum melt viscosities were obtained with polyesters containing 60–70 mole-% PHB. Higher oxygen indicies (39–40) and heat deflection temperatures (150–220°C) were obtained with 80–90 mole-% PHB.     

低分子量芳香族热致液晶聚（对羟基苯甲酸－对苯二甲酸双酚A酯）的研究

 借酯交换反应，以对羟基苯甲酸、对苯二甲酸和双酚Ａ为单体通过淤浆聚合制备出６个低分子量芳香族热致液晶样品，即ＰＨＢＡ／ＴＰＡ／ＢＰＡ共聚酯．由于此单体含量不同的共聚酯样品在适当的溶剂中有较好的溶解性，故能进行许多表征．根据实验结果还得到了表示转变温度一组成关系的相图，并进行了讨论．     

一种新型阻燃抗熔滴共聚酯的合成及表征

双酚A与碳酸乙烯酯反应得到改性单体双(羟乙基)双酚A(BHEEB),BHEEB与对苯二甲酸、乙二醇及阻燃剂[(6-氧代-6H-二苯并[c,e][1,2]氧磷杂己环-6-基)甲基]丁二酸(DDP)通过无规共聚合成了一种新型阻燃共聚酯PBPET.用1H-NMR、ICP-AES对共聚酯的结构进行了表征,用热重分析(TGA)、氧指数(LOI)测定、垂直燃烧测试等对共聚酯的热稳定性、阻燃性和熔滴行为进行了研究.结果表明,BHEEB可以提高共聚酯的热稳定性,含5 mol%BHEEB与4.8 mol%DDP的共聚酯P4.8B5PET,其TGA测试中600℃下氮气氛残炭(wt6R00)可达18.0%.燃烧测试表明,P4.8B5PET的LOI值可达37.0,垂直燃烧达V-0级,并且改性单体BHEEB的引入还能有效地改善聚酯燃烧时的熔滴行为.     

Synthesis and characterization of biodegradable poly(butylene succinate-co-butylene fumarate)s

A series of aliphatic biodegradable polyesters modified with fumaric residues was synthesized by transesterification in the melt of dimethyl succinate, dimethyl fumarate and 1,4-butanediol. The amount of unsaturation, originating from the fumaric acid residues in the polyesters chains was varied from 5 to 20 mol%. The molecular structure and composition of the polyesters were determined by ¹H NMR spectroscopy. The effects of the content of fumaric residues on the thermal and thermo-oxidative properties of the synthesized polyesters were investigated using differential scanning calorimetry (DSC) and thermogravimetric analysis. The degree of crystallinity was determined by DSC and wide angle X-ray scattering. The degrees of crystallinity of the unsaturated copolyesters were reduced, while the melting temperatures were higher in comparison to poly(butylene succinate). Biodegradation of the synthesized copolyesters was estimated in enzymatic degradation tests using a buffer solution with Rhizopus arrhizus lipase at 37 °C. Although the degree of crystallinity of the copolyesters decreases slightly with increasing unsaturation, the biodegradation is not enhanced suggesting that not only the chemical structure and molecular stiffness but also the morphology of the spherulites has an influence on the biodegradation properties. The highest biodegradability was observed for the copolyesters containing 5 and 10 mol% of fumarate units.     

Synthesis and characterization of polyesters derived from succinic acid, ethylene glycol and 1,3-propanediol

Poly(ethylene succinate) (PES), poly(trimethylene succinate) (PTS) and their copolyesters with various compositions were synthesized through a direct polycondensation reaction with titanium tetraisopropoxide as the catalyst. The results of intrinsic viscosity and GPC have proven successful in preparing high molecular weight polyesters. The compositions and the sequence distributions of the copolyesters were determined by analyses of ¹H NMR and ¹³C NMR spectra. The sequence distributions of ethylene succinate units and trimethylene succinate (TS) units were found to be random. Their thermal properties were characterized using differential scanning calorimeter and thermal gravimetric analyzer. All of the copolymers exhibit a single glass transition temperature (T_g). There is no significant difference in the thermal stability among these polyesters. Wide angle X-ray diffractograms (WAXD) were obtained for polyesters which can be crystallized isothermally. The results of thermal analysis and the WAXD patterns indicate that the incorporation of TS units into PES significantly inhibits the crystallization behavior of PES. Additionally, the crystal pattern of PTS is quite different from that of PES. Dynamic mechanical properties of moldable polyesters were investigated using a Rheometer operated at 1 Hz. Below T_g, the incorporation of TS units into PES results in the decline of storage modulus. Above T_g, the effect of crystallinity on the storage modulus can be found.     

The effect of compositions and combinations of the reactants upon the copolycondensation of isophthalic acid/terephthalic acid with a combination of hydroquinones and bisphenols by tosyl chloride/dimethylformamide/pyridine

Copolycondensation of isophthalic acid (IPA)/terephthalic acid (TPA) with various combinations of 2,2‐bis(4‐hydroxyphenyl)propane (BPA) and hydroquinones (HQs) or bisphenols (BPs) was conducted to study the effects of the compositions of IPA/TPA and of BPA/HQs or BPA/BPs upon the reaction. Different from homopolycondensation of each of diol components examined where most of the reaction was facilitated by lower contents of IPA at about 70 mol %, the copolycondensation was influenced by a combination of diol components. With chlorohydroquinone (ClHQ) or bis(4‐hydroxyphenyl)sulfone (BPS) having a polar chlorine or sulfonyl substituent, the reaction proceeded most satisfactorily at IPA/TPA = 30/70, whereas it was IPA/TPA = 50/50 for the reaction with nonpolar methyl substituted methylhydroquinone (MeHQ). The reaction with 2,2‐bis(3,5‐dichloro‐4‐hydroxyphenyl)propane (TC‐BPA), despite having polar chlorine substituents in TC‐BPA, was not affected by IPA/TPA compositions. Alternatively, from the viewpoint of the compositions of diol components, the reactions containing 30–50 mol % of HQs or BPS yielded better results except for the reaction of IPA/TPA = 70/30, in which higher contents of MeHQ was more favorable. On the basis of sequence distributions of diol components in the resultant copolymers determined by NMR, compositions of IPA/TPA or diol components and combinations of the diols producing random copolymers yielded better results in copolycondensation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1100–1106, 2004     

ABA triblock copolyesters composed of poly(l-lactide) A hard blocks: A comparative study of amorphous and crystalline aliphatic polyesters as B soft blocks

In this article, two series of ABA triblock copolyesters composed of poly(l-lactide) A hard blocks and odd-odd aliphatic polyesters as B soft midblock were prepared and compared by various techniques. The results showed that the block structures could be formed without any detectable transesterification, and the composition and molecular weight of the triblock copolyesters could be well controlled by adjusting the feeding ratio of l-lactide monomer to the polyester macroinitiator. It was found that the thermal properties, crystal structure, and spherulitic morphology of the triblock copolyesters depended on the composition and block length. The impact of amorphous and crystalline midblocks on the mechanical properties was compared and discussed. The triblock copolyesters composed of crystalline midblock showed similar ultimate stress and elongation, but higher tensile modulus and yield stress, in comparison with analogous containing amorphous midblock. The triblock copolyester composed of short PLLA hard block and amorphous aliphatic polyester soft midblock displayed typical elastomeric behavior without yield, which is a promising aliphatic polyester thermoplastic elastomer.     

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.     

Fire‐Safe Polyesters Enabled by End‐Group Capturing Chemistry

Upon heating, polyesters decompose to small molecules and release flammable volatiles and toxic gases, primarily through chain scission of their ester linkages, and therefore exhibit poor fire‐safety properties, thus restricting their applications. Reported herein is an end‐group‐capturing effect of (bis)oxazoline groups, generated from the thermal rearrangement of the N‐(2‐hydroxyphenyl)phthalimide (HPI) moiety which was incorporated into the polyester chain by copolymerization. These copolyesters, as a result, exhibit high efficiency in retarding decomposition by capturing the decomposed products, particularly for the carbonyl‐terminated fragments, thus increasing the fire‐safety properties, such as self‐extinguishing, anti‐dripping, and inhibiting heat release and smoke production. The successful application of this method in both semi‐aromatic and aliphatic polyesters provide promising perspectives to designing versatile fire‐safe polymers.     

Synthesis and characterization of new unsaturated polyesters and copolyesters containing azo groups in the main chain

A new interesting class of linear unsaturated polyesters based on dibenzylidenecycloalkanones have been synthesized by interfacial polycondensation of 4,4^′-azodibenzoyl chloride or 3,3^′-azodibenzoyl chloride with: 2,5-bis(p-hydroxybenzylidene)cyclopentanone I, 2,6-bis(p-hydroxybenzylidene)cyclohexanone II, 2,6-divanillylidenecyclohexanone III, or 2,7-bis(p-hydroxybenzylidene)cycloheptanone IV at ambient temperature. The copolyesters are also synthesized from the monomers I, II, III or IV with the diacid chlorides. The resulting polyesters and their copolyesters were characterized by elemental analyses, IR spectroscopy and solubility. Additionally, inherent viscosity of the polyesters in the range 0.32-0.86 dL g⁻¹ and the inherent viscosity of the copolyesters in the range 0.28-0.65 dL g⁻¹ were determined. The UV-visible spectra of certain polymers were measured in m-cresol solution and showed a characteristic absorption band at 435-473 nm due to n-π^* transition. The thermal properties of the polymers were evaluated by thermo gravimetric analysis and differential scanning calorimetry measurements and correlated with their structural units. The crystallinity of some polyesters and copolyesters were tested. In addition, the electrical properties of all polyesters and copolyesters were measured.     

Influence of chemical structure on physicochemical properties and thermal decomposition of the fully bio-based poly(propylene succinate-co-butylene succinate)s

In this work, two polyesters and four copolyesters were studied. All materials were synthesized to obtain the monomers dedicated for thermoplastic polyurethane elastomers. For this type of PUR, the monomers should characterize by appropriate selected physicochemical properties and macromolecular structure distribution, which depends on synthesis conditions. The study of chemical structure with extensive and knowledgeable analysis of formed macromolecules of synthesized bio-based copolyesters was conducted with the use of FTIR and ¹H NMR spectroscopy and MALDI-ToF mass spectrometry. The results allowed to propose the majority of probable chemical structures of macromolecules formed during synthesis. Moreover, the impact of the structure on the thermal stability of the obtained copolyesters was also determined with the use of thermogravimetric analysis. The temperature of the beginning of thermal decomposition equaled even 330 °C. Furthermore, the results of DSC-TG/QMS coupled method confirmed that all prepared polyesters degraded by α and β-hydrogen bond scission mechanisms.     

Synthesis and characterization of aliphatic-aromatic copolyesters based on Cis-1,3-indanediol

This paper reports the synthesis of new copolyesters which incorporate pure isomer cis-1,3-indanediol as well as aliphatic diols HO-(CH₂) _n -OH. 1,3-propanediol, 1,4-butanediol, 1,7-heptanediol and 1,10-decanediol have been used with aromatic diacid terephthaloyl chloride. The stoichiometric proportion of aromatic-aliphatic diols and diacid used is 0.5/0.5/1. All polyesters have been obtained with yields varying from 60 to 84%. The polymers obtained were characterized by various techniques such as FTIR, viscosities, differential scanning calorimetry, thermogravimetric analysis, X-ray diffraction and scanning electron micrograph. All characterizations show that the polymers exhibit semi-crystalline property.     

含二羟基二苯酮的系列热致液晶共聚酯的合成和表征──Ⅲ．含4，4＇－二羟基二苯砜结构的共聚酯

含二羟基二苯酮的系列热致液晶共聚酯的合成和表征──Ⅲ．含４，４＇－二羟基二苯砜结构的共聚酯董德文，池振国，倪玉山，丁孟贤（中国科学院长春应用化学研究所长春１３００２２）陈玉（东北师范大学分析测试中心长春１３００２４）关键词４，４＇－二羟基二苯酮，热致...     

含二羟基二苯酮的系列热致液晶共聚酯的合成和表征──Ⅲ．含4，4＇－二羟基二苯砜结构的共聚酯

hermotropic liquid crystalline copolyesters were synthsized from his(4-hydroxyphenyl) methanone (BHP), tereplithalic acid (TPA), p-hydroxybenzoic acid (PHB) and dihydroxydiphenyl sulfone(DPS). The properties of the copolyesters were characterized by polarized microscope with a hot stage, wide angle X-ray diffraction and differential scanning calorimetry. The results show that the copolyesters containing the BHP exhibit nematic liquid crystallinity.     

Solid state interchain transesterification reactions in macromolecules

Interchain transesterification reactions (ITR) play an important role in high temperature synthesis of most linear polyesters. For example, polyethylene terephthalate (PET) is prepared commercially by heating and distillation of ethylene glycol from a glycol capped oligomer of PET. In this paper, the potential importance of ITR to effect a much wider range of reactions and process is examined. For example, the ability to control the sequence distribution in linear copolyesters is described. In particular, it is shown that one can induce a random sequence distribution in copolyesters by ITR or, conversely, develop an ordered sequence from a random copolyester again by ITR. In one family of liquid crystalline copolyesters an unusual competition between ordering and a thermal Fries rearrangement is described. A whole new family of crosslinked copolyesters has been developed based on this knowledge of ITR. Solid state processing of cured copolyesters into finished articles by ITR has also been demonstrated. These crosslinked copolyesters can be depolymerized back to the starting oligomers by a reverse ITR, providing for the first time a recyclable thermosetting resin.     

Iterative tandem catalysis of secondary diols and diesters to chiral polyesters

The well-known dynamic kinetic resolution of secondary alcohols and esters was extended to secondary diols and diesters to afford chiral polyesters. This process is an example of iterative tandem catalysis (ITC), a polymerization method where the concurrent action of two fundamentally different catalysts is required to achieve chain growth. In order to procure chiral polyesters of high enantiomeric excess value (ee) and good molecular weight, the catalysts employed need to be complementary and compatible during the polymerization reaction. We here show that Shvo's catalyst and Novozym 435 fulfil these requirements. The optimal polymerization conditions of 1,1'-(1,3-phenylene) diethanol (1,3-diol) and diisopropyl adipate required 2 mol% Shvo's catalyst and 12 mg Novozym 435 per mmol alcohol group in the presence of 0.5 M 2,4-dimethyl-3-pentanol as the hydrogen donor. With these conditions, chiral polyesters were obtained with peak molecular weights up to 15 kDa, an ee value up to 99% and with 1-3 % ketone end groups. Also with the structural isomer, 1,4-diol, a chiral polyester was obtained, albeit with lower molecular weight (8.3 kDa) and slightly lower ee (94%). Aliphatic secondary diols also resulted in enantio-enriched polymers but at most an ee of 46 % was obtained with molecular weights in the range of 3.3-3.7 kDa. This low ee originates from the intrinsic low enantioselectivity of Novozym 435 for this type of secondary aliphatic diols. The results presented here show that ITC can be applied to procure chiral polyesters with good molecular weight and high ee from optically inactive AA-BB type monomers.