Blocked isocyanates and isocyanated soybean oil as new chain extenders for unsaturated polyesters

Two different blocked isocyanates, diphenylmethane–bis‐4,4′‐ethyleneurea and diphenylmethane–bis‐4,4′‐carbamoil–ϵ‐caprolactam, and isocyanated soybean oil were used as chain extenders for low‐molecular‐weight unsaturated polyesters. Oligomeric polyesters (molecular weight = 600–700), taken from a manufacturing process in the sixth hour of a 16‐h polyesterification reaction, were reacted with these chain extenders, and the desired chain lengths (molecular weight = 1000–1500) were obtained in a very short time through the reaction of the chain extenders with the polyester end groups. The increase in the molecular weight was monitored with gel permeation chromatography. The obtained polymers were characterized with Fourier transform infrared and ¹H‐NMR and with styrene solubility and gel time measurements. After dilution with styrene, the polyesters were cured with a radical initiator. The thermal and mechanical properties of the cured polyesters were examined with dynamic mechanical analysis and thermogravimetric analysis tests and then compared to those of a commercially available reference unsaturated polyester. The results show that unsaturated polyesters can be chain‐extended with these compounds to shorten the polyesterification time substantially without alterations of the styrene solubility or gel time of the polyesters. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Chain extension reaction in solid‐state polymerization of recycled PET: The influence of 2,2′‐bis‐2‐oxazoline and pyromellitic anhydride

Conventional and chain extended‐modified solid‐state polymerization (SSP) of postconsumer poly(ethylene terephthalate) (PET) from beverage bottles was investigated. SSP was carried out at several temperatures, reaction times, and 2,2′‐bis‐2‐oxazoline (OXZ) or pyromellitic anhydride (ANP) concentrations. The OXZ was added by impregnation with chloroform or acetone solution. Higher molecular weights were reached when the reaction was carried out with OXZ, resulting in bimodal distribution. The molecular weights of the flakes reacted at 230°C for 4 h were 85,000, 95,000, and 100,000 for samples impregnated with 0, 0.5, and 1.25 wt % OXZ solution, respectively. In the case of reactions with ANP, branched chains were obtained. The thermal and thermal‐mechanical‐dynamic properties of these high‐molecular‐weight recycled PET were determined. For OXZ‐reacted samples, the reduction of crystallinity was observed as the reaction time was increased, becoming evident the destruction of the crystalline phase. The chain extended samples did not show changes in thermal relaxations or thermal degradation behavior. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Chain extenders for polyesters. I. Addition-type chain extenders reactive with carboxyl end groups of polyesters

Effective chain extenders for linear polyesters were investigated among some bis-heterocycles, which were capable of coupling carboxyl terminals of the polyesters through addition reaction. Consequently, 2,2′-bis(2-oxazoline), 2,2′-bis(5,6-dihydro-4H-1,3-oxazine) and N,N′-hexamethylenebis(carbamoyl-2- oxazoline) were found to be the most effective chain extenders. Starting from a poly(ethylene terephthalate) (PET) having intrinsic viscosity ([η]) of 0.66 and carboxyl content (CV) of 46 eq/10⁶ g, one could obtain polyesters with [η] of above 1.0 and CV of below 5 eq/10⁶ g in the presence of the chain extenders. Typical reaction condition for the coupling of PET was heating PET under atmospheric nitrogen above its melting temperature with 0.5 mol % of a chain extenders only for several minutes. Bis-2-thiazolines showed no effect under the condition investigated, while in case of bis-2-imidazolines definite degradation was observed. Bis-N-acylaziridines and bisiminocarbonates resulted in some gell formation, indicative of side reactions.     

Impact of the chain extension of poly(ethylene terephthalate) with 1,3‐phenylene‐bis‐oxazoline and N,N′‐carbonylbiscaprolactam by reactive extrusion on its properties

In this article, the material properties of chain extended poly(ethylene terephthalate) (PET) by application of the chain extenders, 1,3‐phenylene‐bis‐oxazoline (1,3‐PBO), N,N′‐carbonylbiscaprolactam (CBC), and combinations thereof are investigated aiming at an application during fiber production from postconsumer PET. The chain extension is performed in one step by a reactive extrusion process. The chain extenders are linearly linked to the COOH and/or OH terminal groups of PET. The influence of the chain extension on the properties of PET is analyzed by measurement of the inherent viscosity, size exclusion chromatography, and carboxyl end‐group titration. Furthermore, the impact of the chain extension on the thermal and rheological properties of PET is studied in detail by differential scanning calorimetry and rheology. The results demonstrate that chain extenders have impact on the properties of PET in dependence on their chemical composition and concentration. The improvement of the molecular weight of the obtained compounds is achieved in an effective and economical approach by the addition of small concentrations of chain extenders (0.2 wt% 1,3‐PBO or 0.3 wt% CBC) without significant negative impact on the properties of PET. POLYM. ENG. SCI., 59:284–294, 2019. © 2018 Society of Plastics Engineers     

Chain extenders for polyester. II. Reactivities of carboxyl-addition-type chain extenders; bis cyclic-imino-ethers

The reaction behavior of such bis cyclic-imino-ethers as 2, 2′-bis(2-oxazoline), which had been proved in the previous paper to be an effective chain extender to couple carboxyl terminals of linear polyesters through addition reaction, has been studied to evaluate their practical applicability as the chain extenders for poly(ethylene terephthalate) and poly(butylene terephthalate). It has been observed that a wide range of excess use of 2,2′-bis(2-oxazoline) resulted in polyesters of almost similar molecular weight. In addition, when excess amounts of the chain extender were added and the reaction conditions were fixed, the ratio of the coupled carboxyl terminals to the initial carboxyl terminals became constant regardless of the initial molecular weight and carboxyl content (CV). The results indicate that the chain-extended polyesters possess predetermined molecular weight and CV, both of which depend only on the molecular weight and CV of the initial polymers, and not on the amount of the chain extender added.     

Chain extension reactions of unsaturated polyesters with epoxy compounds

Unsaturated polyesters (UPE) were chain extended with three different epoxy group containing compounds. The molecular weight increase was monitored using gel permeation chromatography (GPC). The polymers obtained were characterized by FTIR and ¹H NMR, and styrene solubility and gel time. The polyesters were then diluted with styrene and cured with a radical initiator and compared with a commercial reference polyester. Thermal and mechanical properties of the cured polyesters were characterized by dynamic mechanical analysis (DMA) and thermal gravimetric analysis (TGA). The results show that UPE can be chain extended with epoxy containing compounds which substantially shortens the condensation polymerization during manufacture, without compromising their thermal and mechanical properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Catalyzed chain extension of poly(butylene adipate) and poly(butylene succinate) with 2,2′‐(1,4‐phenylene)‐bis(2‐oxazoline)

Low‐molecular‐weight HOOC‐terminated poly(butylene adipate) prepolymer (PrePBA) and poly(butylene succinate) prepolymer (PrePBS) were synthesized through melt‐condensation polymerization from adipic acid or succinic acid with butanediol. The catalyzed chain extension of these prepolymers was carried out at 180–220°C with 2,2′‐(1,4‐phenylene)‐bis(2‐oxazoline) as a chain extender and p‐toluenesulfonic acid (p‐TSA) as a catalyst. Higher molecular weight polyesters were obtained from the catalyzed chain extension than from the noncatalyzed one. However, an improperly high amount of p‐TSA and a high temperature caused branching or a crosslinking reaction. Under optimal conditions, chain‐extended poly(butylene adipate) (PBA) with a number‐average molecular weight up to 29,600 and poly(butylene succinate) (PBS) with an intrinsic viscosity of 0.82 dL/g were synthesized. The chain‐extended polyesters were characterized by IR spectroscopy, ¹H‐NMR spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis, wide‐angle X‐ray scattering, and tensile testing. DSC, wide‐angle X‐ray scattering, and thermogravimetric analysis characterization showed that the chain‐extended PBA and PBS had lower melting temperatures and crystallinities and slower crystallization rates and were less thermally stable than PrePBA and PrePBS. This deterioration of their properties was not harmful enough to impair their thermal processing properties and should not prevent them from being used as biodegradable thermoplastics. The tensile strength of the chain‐extended PBS was about 31.05 MPa. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of aliphatic polyesteramides mainly composed of alternating diester diamide units from N,N′‐bis(2‐Hydroxyethyl)‐oxamide and diacids

This article provided a convenient method to synthesize aliphatic polyesteramides mainly composed of alternating diester diamide units by polycondensation and chain extension. Two kinds of polyesteramide prepolymers were prepared through melt polycondensation from N,N'‐bis(2‐hydroxyethyl)oxamide and adipic acid or sebacic acid. Chain extension of them was conducted with 2,2′‐(1,4‐phenylene)‐bis(2‐oxazoline) and adipoyl biscaprolactamate as combined chain extenders. The chain extended polyesteramides (ExtPEAs) were characterized by IR, ¹H NMR, differential scanning calorimetry, thermogravimetric analysis, wide‐angle X‐ray scattering, tensile test, and dynamic thermomechanical analysis. The results showed that the ExtPEA(0, m)s were mainly constituted with the diester oxamide alternating units. They had T_m above 140.8°C and the initial decomposition temperature above 298.0°C. They crystallized in similar crystallites to Nylon‐66 and were thermoplastic materials with tensile strength up to 31.47 MPa. POLYM. ENG. SCI., 54:756–765, 2014. © 2013 Society of Plastics Engineers     

Curing reaction of saturated aliphatic polyester modified unsaturated polyester resins

Two series of unsaturated polyesters (UPE from isophthalic acid, fumaric acid, and propylene glycol) were prepared. In series-A resins, UPEs wee thickened with isocyanate-terminated saturated aliphatic polyestes, i.e., an isocyanate-terminated polycaprolactone diol (PE-di-OL), through reaction of the isocyanate group with the hydroxyl group of the UPE. In series-B resins, the UPEs were mixed with saturated aliphatic polyesters i.e., PE-di-OL. The curing reaction of these two series of UPEs with styrene was studied by using differential scanning calorimetry (DSC) and gel permeation chromatography (GPC). The DSC data show that for a fixed PE-di-OL molecular weight, the curing reaction rate of series-A UPE is faster than that of series-B UPE. The variation of microgel size during curing ws studied by GPC. These results revealed that microgel formation has a great effect on the kinetics of cure for the unsaturated polyester-styrene system. The curing of these two series of UPEs is found to strongly depend on the compatibility of the components in the curing system.     

Synthesis and characterization of segmented poly(ether ester amide)s from diglycol,adipic acid,and a nylon‐6 oligomer

This article presents a convenient method for synthesizing segmented poly(ether ester amide)s (PEEAs) by polycondensation and chain extension. A nylon‐6 oligomer prepared from ε‐caprolactam and ethanolamine through ring‐opening polymerization was polymerized with adipic acid and diglycol to prepare PEEA prepolymers (PrePEEAs) with ether linkages and amide contents ranging from 20 to 60 mol%. Chain extension of the PrePEEAs was conducted at 200°C using 2,2′‐(1,4‐phenylene)‐bis(2‐oxazoline) and carbonyl biscaprolactamate as combination chain extenders. The chain‐extended PEEAs (ExtPEEAs) were characterized by viscometry, gel permeation chromatography, FT‐IR, ¹H‐NMR, differential scanning calorimetry, thermogravimetric analysis, wide angle X‐ray diffraction, and tensile testing. Results show that incorporation of nylon‐6 segments yields semicrystalline ExtPEEAs and that introduction of ether linkages improves the flexibility of the resultant polymers. ExtPEEAs showed T_m from 107.6 to 137.3°C, good thermal stability with initial decomposition temperatures above 337.3°C, and tensile strengths of up to 27.4 MPa with strains at break ranging from 231.24 to 1052.52%. POLYM. ENG. SCI., 55:763–770, 2015. © 2014 Society of Plastics Engineers     

Low‐modulus siloxane–polyurethanes. Part II. Effect of chain extender structure on properties and morphology

A series of six polyurethanes were prepared to study the effect of silicon chain extender structure on properties and morphology of siloxane–polyurethanes. Polyurethanes were prepared by a two‐step bulk polymerization without a catalyst. The soft segment of the polyurethanes was based on an 80:20 (w/w) mixture of α,ω‐bis(6‐hydroxyethoxypropyl) polydimethylsiloxane (PDMS, MW 966) and poly(hexamethylene) oxide (MW 714). The hard segment was based on 4,4′‐methylenediphenyl diisocyanate (MDI) and a 60:40 molar mixture of 1,4‐butanediol (BDO) and a silicon chain extender. Silicon chain extenders (SCE) investigated were 1,3‐bis(4‐hydroxybutyl)1,1,3,3‐tetramethyldisiloxane (BHTD), 1,3‐bis(3‐hydroxypropyl)1,1,3,3‐tetramethyldisiloxane (BPTD), 1,4‐bis(3‐hydroxypropyl)1,1,3,3‐tetramethyldisilylethylene (HTDE), 1,3‐bis(6‐hydroxyethoxypropyl)1,1,3,3‐tetramethyldisiloxane (BETD). All polyurethanes were clear and transparent with number average molecular weights between 72,000 to 116,000. Incorporation of the silicon chain extender resulted in polyurethanes with low‐modulus and high elongation. This was achieved without significant compromise in ultimate tensile strength in all cases, except BETD. Differential scanning calorimetry (DSC) results showed that the silicon chain extenders did not significantly disrupt the hard segment crystallinity, but exhibited a unique morphological feature where SCE‐based hard segments formed separate domains, which may be the primary reason for achieving low modulus without significant compromise in strength. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1092–1100, 2003     

Polyesters containing sulfur. I. Products of melt polycondensation of diphenylmethane-4,4′-di(methylthioacetic acid) with some diols

Several new polyesters containing sulfur in the main chain were obtained by melt polycondensation of diphenylmethane-4,4′-di(methylthioacetic acid) with ethanediol, 1,3-propane diol, 1,4-butanediol, 1,5-pentenediol, 1,6-hexanediol, 1,2-propanediol, and 2,2′-oxydiethanol. The structure of all polyesters was determined from elemental analysis and infrared (IR) spectra. Yield, reduced viscosity, molecular weight, and softening temperature for reaction products have been found. Initial decomposition and initial intensive decomposition temperature were defined from the curves of thermogravimetric analysis.     

Effect of chain extender structure on the properties and morphology of polyurethanes based on H12MDI and mixed macrodiols (PDMS–PHMO)

The effect of chain extender structure on properties and morphology of α,ω‐bis(6‐hydroxyethoxypropyl) polydimethylsiloxane (PDMS) and poly(hexamethylene oxide) (PHMO) mixed macrodiol‐based aliphatic polyurethane elastomers was investigated using tensile testing, differential scanning calorimetry (DSC), and dynamic mechanical thermal analysis (DMTA). All polyurethanes were based on 50 wt % of hard segment derived from 4,4′‐methylenecyclohexyl diisocyanate (H₁₂MDI) and a chain extender mixture. 1,4‐Butanediol was the primary chain extender, while one of 1,3‐bis(4‐hydroxybutyl)tetramethyldisiloxane (BHTD), 1,3‐bis(3‐hydroxypropyl)tetramethyldisiloxane (BPTD), hydroquinonebis(2‐hydroxyethyl)ether (HQHE), 1,3‐bis(3‐hydroxypropyl)tetramethyldisilylethylene (HTDE), or 2,2,3,3,4,4‐hexafluoro‐1,5‐pentanediol (HFPD) each was used as a secondary chain extender. Two series of polyurethanes containing 80 : 20 (Series A) and 60 : 40 (Series B) molar ratios of primary and secondary chain extenders were prepared using one‐step bulk polymerization. All polyurethanes were clear and transparent and had number‐average molecular weights between 56,000 and 122,100. Incorporation of the secondary chain extender resulted in polyurethanes with low flexural modulus and high elongation. Good ultimate tensile strength was achieved in most cases. DSC and DMTA analyses showed that the incorporation of a secondary chain extender disrupted the hard segment order in all cases. The highest disruption was observed with HFPD, while the silicon‐based chain extenders gave less disruption, particularly in Series A. Further, the silicon chain extenders improved the compatibility of the PDMS soft segment phase with the hard segment, whereas with HFPD and HQHE, this was not observed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2979–2989, 1999     

Polybutadiene/polyhedral oligomeric silsesquioxane nanohybrid: investigation of various reactants in polyesterification reaction

Nano‐sized polyhedral oligomeric silsesquioxane (POSS) diol or ethylene glycol (EG) as diol monomer was incorporated into hydroxyl‐terminated polybutadiene (HTPBD) chain in the presence of fumaryl or thionyl chloride as extenders. Using these polyesterification reactions, two fumarate‐based polyesters and two polyester sulfites were synthesized. Each couple of polyesters and polyester sulfites includes a linear (diol:EG) and a nanohybrid macromer (diol:POSS). Full structural characterization was performed using Fourier transform infrared, ¹H NMR and ¹³C NMR spectroscopies. Gel permeation chromatography was undertaken to study polyesterification mechanisms by deconvolution of the obtained traces. Finally, differential scanning calorimetry, thermogravimetric analysis and cell culture were performed to evaluate the structure–property relationship for the synthesized macromers in comparison with unreacted HTPBD. © 2016 Society of Chemical Industry     

Reaction of phenol‐ and thiophenol‐terminated compounds with bisoxazolines

Bulk reactions of phenolic compounds (bisphenol‐A and α,ω‐diphenol oligosulfone) or thiols (thiophenol and bis(4‐mercaptophenyl)sulfide) with bisoxazoline coupling agents, namely 2,2'‐(1,3‐phenylene)bis(2‐oxazoline) ( mbox ), 2,2'‐(1,4‐phenylene)bis(2‐oxazoline) ( pbox ), and 2,2'‐(2,6‐pyridylene)bis(2‐oxazoline) ( pybox ), were carried out in the bulk at 140–240°C. The reactions were followed by viscosimetry, size exclusion chromatography, and ¹H‐ and ¹³C‐NMR spectroscopy. The phenol/bisoxazoline bulk reactions at 240°C required the presence of sodium methoxide catalyst. Bisoxazoline pybox gave the best results in this case. Thiol and dithiol/bisoxazoline reactions were faster and did not require any catalyst. High‐molar‐mass polymers were obtained within 5 min at 200°C while using bis(4‐mercaptophenyl)sulfide (BMPS) and any of the bisoxazolines. The NMR spectra of model compounds and polymers were fully assigned, showing that the oxazoline/phenol and oxazoline/thiophenol (tph) polyaddition reactions proceed in the expected way, without any noticeable side reaction. All polymers were amorphous and displayed good thermal stability. Bisoxazolines were also used as coupling agents for the preparation of copolymers of BMPS and α,ω‐dicarboxy polyamide‐12 and for the preparation of polysulfone‐polyamide‐12 block copolymers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Chain‐extended polyurethanes—Synthesis and characterization

Chain‐extended polyurethanes (PUs) were prepared using castor oil and different diisocyanates such as toluene‐2,4‐diisocyanate and 4,4′‐methylene bis(phenylisocyanate) as a crosslinker and different aromatic diamines like 4,4′‐diaminodiphenyl methane and 4,4′‐diaminodiphenyl sulphone as chain extenders. The effect of aromatic diamines on the swelling and thermal degradation behavior of PU have been discussed. A thermogravimetric analyzer (TGA) curve shows that all the chain‐extended PUs are stable up to 194°C and that maximum weight loss occurs at 490°C. The TGA thermograms show that the thermal degradation of the PUs was found to proceed in two steps. The average molecular weight between crosslinks (M?_c) was determined by swelling studies. The properties imparted by the aromatic chain extenders are explained on the basis of groups present in the diamines. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 359–369, 2002; DOI 10.1002/app.10347     

Synthesis and characterization of polyesters based on 1,1,1‐[bis(4‐hydroxyphenyl)‐4′‐pentadecylphenyl]ethane

Aromatic polyesters are of considerable interest because of their excellent mechanical properties, chemical resistance and thermal stability. However, most aromatic polyesters are difficult to process due to their high glass transition temperatures coupled with their insolubility in common organic solvents. The present article describes a series of organosoluble polyesters and copolyesters based on 1,1,1‐[bis(4‐hydroxyphenyl)‐4′‐pentadecylphenyl]ethane. A series of new aromatic polyesters containing pendant pentadecyl chains was synthesized by interfacial polycondensation of 1,1,1‐[bis(4‐hydroxyphenyl)‐4′‐pentadecylphenyl]ethane with terephthalic acid chloride (TPC), isophthalic acid chloride (IPC) and a mixture of TPC and IPC. A series of copolyesters was synthesized from 4,4′‐isopropylidenediphenol with TPC by incorporating 1,1,1‐[bis(4‐hydroxyphenyl)‐4′‐pentadecylphenyl]ethane as a comonomer. Inherent viscosities of the polyesters and copolyesters were in the range 0.72–1.65 dL g^?1 and number‐average molecular weights were in the range 18 170–87 220. The polyesters and copolyesters containing pendant pentadecyl chains dissolved readily in organic solvents such as chloroform, dichloromethane, pyridine and m‐cresol and could be cast into transparent, flexible and apparently tough films. Wide‐angle X‐ray diffraction data revealed the amorphous nature of the polyesters and copolyesters. The formation of loosely developed layered structure was observed due to the packing of pendant pentadecyl chains. The temperature at 10% weight loss, determined using thermogravimetric analysis in nitrogen atmosphere, of the polyesters and copolyesters containing pendant pentadecyl chains was in the range 400–460 °C. The polyesters and copolyesters exhibited glass transition temperatures in the range 63–82 °C and 177–183 °C, respectively. Copyright © 2010 Society of Chemical Industry     

Effect of Two‐Step Chain Extension using Joncryl and PMDA on the Rheological Properties of Poly (lactic acid)

This research considers a two‐step chain extension reaction in the presence of two chain extenders, Joncryl and Pyromellitic dianhydride (PMDA), as a solution for poor melt properties of poly (lactic acid) (PLA). The aim of adding PMDA is to increase the carboxyl groups via the anhydride ring‐opening reaction so that the reaction between PLA and Joncryl could be facilitated since the reactivity between the epoxy and carboxyl group is more than epoxy and hydroxyl group. The reactions are confirmed by measuring the acid value, and a two‐step reaction mechanism is suggested. Shear and elongational rheological properties of the samples are investigated; furthermore, gel permeation chromatography analyses and tensile tests are exploited for studying the molecular weight and tensile properties, respectively. The results show that the chain extension reactions lead to an increase in the storage modulus, complex viscosity, and molecular weight. Also, the PLA chains which are extended utilizing both chain extenders simultaneously evince a synergistic improvement in the shear and elongational rheological properties due to longer segments between branching points on the structure.     

Chain extenders for polyesters. V. Reactivities of hydroxyl-addition-type chain extender; 2,2′-bis(4h-3,1-benzoxazin-4-one)

In our previous study,¹ 2,2′-bis(4H-3,1-benzoxazin-4-one) (BNZ) was found to be most effective among the tested chain extenders in coupling hydroxyl terminals of linear polyesters through addition reaction. Detailed studies on BNZ chemistry have been made using poly(ethylene terephthalate) and poly(butylene terephthalate) as the polyester. It has been observed that use of BNZ, equivalent amount to the hydroxyl terminals of the initial polymer, resulted in the highest molecular weight. In contrast with the case of 2,2′-bis(2-oxazoline), which was found to be the most effective carboxyl-addition type chain extender and a wide range of its excess use was allowed,^2,3 an excessive use of BNZ resulted in lower molecular weight polymer. Thus, when an equivalent amount of BNZ to the hydroxyl terminals was used, the molecular weight of the resulting polymer could be determined by the carboxyl content of the initial polymer, regardless of its initial molecular weight.     

Chain extenders for polyesters. IV. Properties of the polyesters chain-extended by 2,2′-bis(2-oxazoline)

Some properties of the polyesters treated with such an addition-type chain extender as 2,2′-bis(2-oxazoline) (BOZ) have been investigated. The molecular size distribution and the melting point of the resultant polyesters indicate that BOZ reacts to form linear chain-extended polymers without branching. As for their thermal stabilities, unreacted oxazoline remained in the polymer can act as a heat stabilizer by further reacting with carboxyl terminals of the polymers and by preventing decrease in the molecular weight even in the solid state. On the other hand, BOZ unit incorporated in the polyester chain was relatively thermally unstable compared with the ordinary polyester chain, especially under the polyester melt condition. The polyester treated with BOZ has a rather low carboxyl content, and considerable improvement in the hydrolytic stability has been observed. But unreacted oxazoline groups adversely affected the hydrolytic stability, although the effect was about eight times as small as that of carboxyl groups.