Crystallization kinetics of poly(1,4‐butylene‐co‐ethylene terephthalate)

The crystallization kinetics of poly(butylene terephthalate) (PBT), poly(ethylene terephthalate) (PET), and their copolymers poly(1,4‐butylene‐co‐ethylene terephthalate) (PBET) containing 70/30, 65/35 and 60/40 molar ratios of 1,4‐butanediol/ethylene glycol were investigated using differential scanning calorimetry (DSC) at crystallization temperatures (T_c) which were 35–90 °C below equilibrium melting temperature . Although these copolymers contain both monomers in high proportion, DSC data revealed for copolymer crystallization behaviour. The reason for such copolymers being able to crystallize could be due to the similar chemical structures of 1,4‐butanediol and ethylene glycol. DSC results for isothermal crystallization revealed that random copolymers had a lower degree of crystallinity and lower crystallite growth rate than those of homopolymers. DSC heating scans, after completion of isothermal crystallization, showed triple melting endotherms for all these polyesters, similar to those of other polymers as reported in the literature. The crystallization isotherms followed the Avrami equation with an exponent n of 2–2.5 for PET and 2.5–3.0 for PBT and PBETs. Analyses of the Lauritzen–Hoffman equation for DSC isothermal crystallization data revealed that PBT and PET had higher growth rate constant G_o, and nucleation constant K_g than those of PBET copolymers. © 2001 Society of Chemical Industry     

Effects of shearing and comonomer content on the crystallization behavior of poly(butylene succinate‐co‐butylene 2‐ethyl‐2‐methyl succinate)

Poly(butylene succinate‐co‐butylene 2‐ethyl‐2‐methyl succinate) (PBSEMS) random copolymers were prepared with different comonomer compositions. The effects of shearing and comonomer content on the crystallization behavior of these copolymers were investigated at 80 °C. The thermal and morphological properties of the resulting samples were also discussed. The copolymers showed a longer induction time and a slower crystallization rate with increasing comonomer content. The promoting effect of shear on the overall crystallization behavior was more notable for those copolymers containing more 2‐ethyl‐2‐methyl succinic acid (EMSA) units. The melting temperature of ‘as‐prepared’ poly(butylene succinate) (PBS) was ca. 115 °C, while that of the copolymers varied from 112 to 102 °C. Higher comonomer contents in the copolymers gave rise to lower melting temperatures and broader melting peaks. In addition, the isothermally crystallized samples showed multiple melting endothermic behavior, the extent of which depended on the comonomer content. The copolymers showed different wide‐angle X‐ray diffraction (WAXD) patterns from that of neat PBS, depending on the comonomer content and shear applied during crystallization. With increasing comonomer content, the copolymers crystallized without shearing, showing the shifting of a diffraction peak to a higher angle, while those crystallized under shear did not show any peak shift. Copyright © 2004 Society of Chemical Industry     

Properties of uncompatibilized and compatibilized poly(butylene terephthalate)–LLDPE blends

In this work, blends of poly(butylene terephthalate) (PBT) and linear low‐density polyethylene (LLDPE) were prepared. LLDPE was used as an impact modifier. Since the system was found to be incompatible, compatibilization was sought for by the addition of the following two types of functionalized polyethylene: ethylene vinylacetate copolymer (EVA) and maleic anhydride‐grafted EVA copolymer (EVA‐g‐MAH). The effects of the compatibilizers on the rheological and mechanical properties of the blends have been also quantitatively investigated. The impact strength of the PBT–LLDPE binary blends slightly increased at a lower concentration of LLDPE but increased remarkably above a concentration of 60 wt % of LLDPE. The morphology of the blends showed that the LLDPE particles had dispersed in the PBT matrix below 40 wt % of LLDPE, while, at 60 wt % of LLDPE, a co‐continuous morphology was obtained, which could explain the increase of the impact strength of the blend. Generally, the mechanical strength was decreased by adding LLDPE to PBT. Addition of EVA or EVA‐g‐MAH as a compatibilizer to PBT–LLDPE (70/30) blend considerably improved the impact strength of the blend without significantly sacrificing the tensile and the flexural strength. More improvement in those mechanical properties was observed in the case of the EVA‐g‐MAH system than for the EVA system. A larger viscosity increase was also observed in the case of the EVA‐g‐MAH than EVA. This may be due to interaction of the EVA‐g‐MAH with PBT. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 989–997, 1999     

Melting behavior and crystallization kinetics of poly(butylene terephthalate‐co‐diethylene terephthalate) and poly(butylene terephthalate‐co‐triethylene terephthalate) copolyesters

The melting behavior of poly(butylene terephthalate‐co‐diethylene terephthalate) and poly(butylene terephthalate‐co‐triethylene terephthalate) copolymers was investigated by differential scanning calorimetry after isothermal crystallization from the melt. Multiple endotherms were found for all the samples, and attributed to the melting and recrystallization processes. By applying the Hoffman‐Weeks' method, the equilibrium melting temperatures of the copolymers under investigation were obtained. Two distinct peaks in the crystallization exothermic curve were observed for all the samples. Both of them appeared at higher times than that of PBT, indicating that the introduction of a comonomer decreased the crystallization rate. The observed dependence of this latter on composition was explained on the basis of the content of ether–oxygen atoms in diethylene and triethylene terephthalate units, and of the different sizes of these units. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3545–3551, 2001     

Preparation of poly(butylene succinate)‐poly[2‐(dimethylamino)ethyl methacrylate] copolymers and their applications as carriers for drug delivery

Copolymers of poly[2‐(dimethylamino)ethyl methacrylate]–poly(butylene succinate)–poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA–PBS–PDMAEMA, PDBD) were synthesized through a chain‐extension reaction. The thermal properties characterized using differential scanning calorimetry showed that the introduction of PDMAEMA chains slightly decreased the melting temperature of PBS. The water contact angle of PDBD copolymer films with media of various pH decreased with a decrease of pH. This should be ascribed to the conformational transition of PDMAEMA blocks from a compact coil to an expanding shape in accordance with the variation of the pH of the surroundings. The results of dynamic light scattering and scanning electron microscopy revealed that PDBD copolymers could form spherical micelles with small particle size and narrow particle size distribution. Furthermore, drug loading (loading content, ca 10%; encapsulation efficiency, ca 60%) and release experiments were conducted using doxorubicin as a hydrophobic model drug. The results of release experiments of copolymer nanomicelles showed that these micelles had pH‐responsive properties. © 2018 Society of Chemical Industry     

Sulfur‐containing polymers: Effect of composition on melting behavior and crystallization kinetics of poly(butylene terephthalate)

The melting behavior and crystallization kinetics of poly(butylene terephthalate/thiodipropionate) (PBT) copolymers were investigated using the differential scanning calorimetry technique. Multiple endotherms typical of PBT were observed in the copolymers under investigation and were found to be influenced both by crystallization temperature (T_c) and composition. Wide‐angle X‐ray diffraction measurements permitted the identification of the crystalline structure of PBT in all the copolymers investigated. By applying the Hoffman–Weeks method, the equilibrium melting temperature of the copolymers was derived. Isothermal crystallization kinetics were analyzed according to Avrami's treatment. Values of the exponent n close to 3 were obtained, independent of T_c and composition, results in agreement with it being a crystallization process originating from predetermined nuclei and characterized by three‐dimensional spherulitic growth. The introduction of butylene thiodipropionate units was found to decrease the PBT crystallization rate. The heat of fusion (ΔH_m) was correlated to the specific heat increment (Δc_p) of samples of different degrees of crystallinity, and the results were interpreted based on there being an interphase, whose amount was found to increase as the sulfur‐containing unit content was increased. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2003–2009, 2003     

Isothermal crystallization kinetics and melting behaviors of poly(butylene terephthalate) and poly(butylene terephthalate‐co‐fumarate) copolymer

The isothermal crystallization kinetics and melting behaviors after isothermal crystallization of poly(butylene terephthalate) (PBT) and poly(butylene terephthalate‐co‐fumarate) (PBTF) containing 95/5, 90/10, and 80/20 molar ratios of terephthalic acid/fumaric acid were investigated by differential scanning calorimetry. The equilibrium melting temperatures of these polymers were estimated by Hoffman–Weeks equation. So far as the crystallization kinetics was concerned, the Avrami equation was applied and the values of the exponent n for all these polymers are in the range of 2.50–2.96, indicating that the addition of fumarate does not affect the geometric dimension of PBT crystal growth. Crystallization activation energy (ΔE) and nucleation constant (K_g) of PBTF copolymers are higher than that of PBT homopolymer, suggesting that the introduction of fumarate hinders the crystallization of PBT in PBTF. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Synthesis and characterization of copolymers based on poly(butylene terephthalate) and ethylene oxide‐poly(dimethylsiloxane)‐ethylene oxide

A series of thermoplastic elastomers based on ethylene oxide‐poly(dimethylsiloxane)‐ethylene oxide (EO‐PDMS‐EO), as the soft segment, and poly(butylene terephthalate) (PBT), as the hard segment, were synthesized by catalyzed two‐step, melt transesterification reaction of dimethyl terephthalate (DMT) with 1,4‐butanediol (BD) and α,ω‐dihydroxy‐(EO‐PDMS‐EO). Copolymers with a content of hard PBT segments between 40 and 90 mass % and a constant length of the soft EO‐PDMS‐EO segments were prepared. The siloxane prepolymer with hydrophilic terminal EO units was used to improve the miscibility between the polar comonomers, DMT and BD, and the nonpolar PDMS. The molecular structure and composition of the copolymers were determined by ¹H‐NMR spectroscopy, whereas the effectiveness of the incorporation of α,ω‐dihydroxy‐(EO‐PDMS‐EO) into the copolymer chains was verified by chloroform extraction. The effects of the structure and composition of the copolymers on the melting temperatures and the degree of crystallinity, as well as on the thermal degradation stability and some rheological properties, were studied. It was demonstrated that the degree of crystallinity, the melting and crystallization temperatures of the copolymers increased with increasing mass fraction of the PBT segments. The thermal stability of the copolymers was lower than that of PBT homopolymer, because of the presence of thermoliable ether bonds in the soft segments. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Miscibilities and rheological properties of poly(butylene succinate)–Poly(butylene terephthalate) blends

An aliphatic/aromatic polyester blend has been dealt with in this study. As an aliphatic polyester, poly(butylene succinate) (PBS) was used, which is thought to possess biodegradability, but it is relatively expensive. It has been blended with poly(butylene terephthalate) (PBT) in order to obtain a biodegradable blend with better mechanical properties and lower cost. The miscibilities of PBS–PBT blends were examined not only from the changes of T_g but also from log G′–log G" plots. Dynamic mechanical thermal analyzer (DMTA) was an appropriate, sensitive method to obtain the glass transitions properly. Thermal stabilities of PBS and PBT were also verified at the temperature of 240°C. A transesterification reaction between two polyesters at 240°C was hardly detectable so that it did not affect the miscibilities and properties of the blends. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 945–951, 1999     

Synthesis and characterization of poly(butylene terephthalate)‐co‐poly(butylene succinate)‐block‐poly(ethylene glycol) segmented block copolymers

Poly(butylene terephthalate)‐co‐poly(butylene succinate)‐block‐poly(ethylene glycol) segmented random copolymers, with poly(butylene succinate) (PBS) molar fraction (M_PBS) varying from 10 to 60 %, were synthesized through a melt polycondensation process and characterized by means of GPC, NMR, DSC and mechanical testing. The number‐average relative molecular mass of the copolymers was higher than 4 × 10⁴ g mol^?1 with polydispersity below 1.9. Sequence distribution analysis on the two types of hard segments by means of ¹H NMR revealed that the number‐average sequence length of PBT decreased from 2.80 to 1.23, while that of PBS increased from 1.27 to 4.76 with increasing M_PBS. The random distribution of hard segments was also justified because of the degree of randomness around 1.0. Micro‐phase separation structure was verified for the appearance of two glass transition temperatures and two melting points, respectively, in DSC thermograms of most samples. The crystallinity of hard segments changed with the crystallizability controlled by the average sequence length and reached the minimum value at an M_PBS of about 50–60 mol%. The results can also be ascribed to the co‐crystallization between two structurally analogous hard segments. Mechanical testing results demonstrated that incorporating a certain amount of PBS moieties (less than 30 mol%), at the expense of a minute depression of the elastic modulus, that higher relative elongation and more flexibility of polymer chain could be expected. Maximum equilibrium water absorption and faster degradation rates were observed on samples with higher M_PBS values and lower crystallinity of hard segments were better hydrophilicity of the polymer chain, through in vitro degradation experiments. Copyright © 2003 Society of Chemical Industry     

Syntheses and characterization of poly(butylene terephthalate) copolyesters modified with p‐acetoxybenzoic acid

Poly(butylene terephthalate) (PBT) copolyesters modified with seven compositions of p‐acetoxybenzoic acid (PABA) ranging from 10 to 70 mol % were prepared. The X‐ray diffraction patterns, the polarizing microscopy behaviors, and thermal analysis showed that the modified PBT contained more PABA homopolymer units (PABA–PABA) than PBT–PABA units in the copolyesters. On increasing PABA mole percenage, PBT crystallinity decreased and thermal stability increased. It was found that although the PBT copolyesters did not exhibit a clear liquid crystalline texture like the copolyester of poly(ethylene terephthalate) modified with PABA did, the PBT copolyester containing 70 mol % of PABA exhibited the typical shear thinning behavior of a liquid crystalline polymer. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1085–1095, 2001     

Synthesis and characterization of poly(butylene terephthalate‐co‐triethylene terephthalate) copolyesters

Poly(butylene terephthalate‐co‐triethylene terephthalate) random copolymers of various compositions and molecular weights were synthesized in bulk and characterized in terms of their chemical structure and thermal and rheological properties. At room temperature all the copolymers were partially crystalline and showed good thermal stability. The main effect of copolymerization was a decrease in the melting and glass‐transition temperatures with respect to the poly(butylene tere‐ phthalate) homopolymer. The fusion temperatures were well correlated with the composition by the Baur equation and the equilibrium melting temperature and the heat of fusion extrapolated values for poly(butylene terephthalate) were in good agreement with those reported elsewhere. Triethylene terephthalate units were found to influence the rheological behavior in the melt, the viscosity being significantly higher than that of the poly(butylene terephthalate‐co‐diethylene terephthalate) copolymers investigated previously. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 981–990, 2001     

Preparation and thermal behavior of random poly(butylene terephthalate/azelate) copolyesters

Poly(butylene terephthalate), poly(butylene azelate), and poly(butylene terephthalate/butylene azelate) random copolymers of various compositions were synthesized in bulk using the well‐known two‐stage polycondensation procedure, and characterized in terms of chemical structure and molecular weight. The thermal behavior was examined by thermogravimetric analysis and differential scanning calorimetry. As far as the thermal stability is concerned, it was found to be rather similar for all copolymers and homopolymers investigated. All the copolymers were found to be partially crystalline, and the main effect of copolymerization was a lowering in the amount of crystallinity and a decrease of melting temperature with respect to pure homopolymers. Flory's equation was found to describe the T_m–composition data and permitted to calculate the melting temperatures (T^°_m ) and the heats of fusion (ΔH_u) of both the completely crystalline homopolymers. Owing to the high crystallization rate, the glass transition was observable only for the copolymers containing from 30 to 70 mol % of the terephthalate units; even though the samples cannot be frozen in a completely amorphous state, the data obtained confirmed that the introduction of the aromatic units gave rise to an increase of T_g, due to a chain stiffening. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2694–2702, 1999     

Fabrication of micelles from poly(butylene succinate) and poly(2‐methacryloyloxyethyl phosphorylcholine) copolymers as a potential drug carrier

A series of copolymers of poly(2‐methacryloyloxyethyl phosphorylcholine)‐b‐poly(butylene succinate)‐b‐poly(2‐methacryloyloxyethyl phosphorylcholine) (PMPC‐b‐PBS‐b‐PMPC) were synthesized by atom transfer radical polymerization. The structure of the polymers was characterized by ¹H NMR and infrared spectroscopy, and their thermal properties were described using TGA and DSC. In aqueous solutions, the PMPC‐b‐PBS‐b‐PMPC could form micelles with sizes ranging from 108 to 170 nm. In vitro release studies showed that acidic media and a longer PMPC chain benefited doxorubicin (DOX) release. 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide (MTT) assays indicated that the micelles had low cytotoxicity to HeLa and L929 cells. DOX‐loaded micelles exhibited high cytotoxicity to HeLa cells. Flow cytometry results demonstrated that DOX‐loaded micelles could be internalized by HeLa cells. The in vitro phagocytosis results showed 3.9‐fold and 5.5‐fold reductions compared with poly(lactic acid) (PLA) nanoparticles and PDS55 micelles. These results demonstrate that PMPC‐b‐PBS‐b‐PMPC block copolymer micelles have great promise for cancer therapy. © 2017 Society of Chemical Industry     

Depolymerization of poly(butylene terephthalate) using high‐temperature and high‐pressure methanol

Poly(butylene terephthalate) (PBT) was depolymerized in excess methanol at high‐temperature (473–523 K) and high‐pressure (4–14 MPa) conditions. Considering the critical point of methanol (512.6 K, 8.09 MPa), the reaction pressure was varied over the range of 6–14 MPa at the reaction temperature of 513 K. As a result, ca. 20 min was required to recover dimethyl terephthalate and 1,4‐butanediol, quantitatively, at any pressure, indicating that the supercritical state of methanol is not a key factor of degradation of PBT and that the effect of pressure is little. On the contrary, when the reaction temperature was varied over the range of 473–523 K at the pressure 12 MPa, the decomposition rate constant of PBT at the reaction temperatures (503–523 K) higher than the melting temperature of PBT (500 K) was much higher than that at 473–483 K. This result indicates that melting of PBT is an important factor for the short‐time depolymerization of PBT. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3228–3233, 2000     

Rheological and thermal properties of blends of modified poly(ethylene terephthalate) with p‐acetoxybenzoic acid and poly(butylene terephthalate)

Blending of thermotropic liquid crystalline polyesters (LCPs) with conventional polymers could result in materials that can be used as an alternative for short fiber‐reinforced thermoplastic composites, because of their low melt viscosity as well as their inherent high stiffness and strength, high use temperature, and excellent chemical resistance and low coefficient of expansion. In most of the blends was used LCP of 40 mol % of poly(ethylene terephthalate) (PET) and 60 mol % of p‐acetoxybenzoic acid (PABA). In this work, blends of several copolyesters having various PABA compositions from 10 to 70 mol % and poly(butylene terephthalate) (PBT) were prepared and their rheological and thermal properties were investigated. For convenience, the copolyesters were designated as PETA‐x, where x is the mol % of PABA. It was found that PET‐60 and PET‐70 copolyesters decreased the melt viscosity of PBT in the blends and those PBT/PETA‐60 and PBT/PETA‐70 blends showed different melt viscosity behaviors with the change in shear rate, while blends of PBT and PET‐x having less than 50 mol % of PABA exhibited totally different rheological behaviors. The blends of PBT with PETA‐50, PETA‐60, and PETA‐70 showed the morphology of multiple layers of fibers. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1797–1806, 1999     

Synthesis and characterizations of branched poly(butylene succinate) copolymers with 1,2‐octanediol segments

Branched poly(butylene succinate) (PBS) copolymers were synthesized, from succinic acid (SA), 1,4‐butanediol (1,4‐BD), and 1,2‐octanediol (1,2‐OD) through a two‐step process containing esterification and polycondensation, with different mole fractions of 1,2‐OD segments. The branched PBS copolymers were characterized with ¹H‐NMR, differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD), thermogravimetric analysis (TGA), dynamic rheological testing, and tensile properties analysis. The results of DSC and WAXD show that, with the increasing of the 1,2‐OD segments content, the glass transition temperature (T_g), melting temperature (T_m), crystallization temperature (T_c), and the degree of crystallinity (X_c) decrease. While the crystal structure of PBS does not change by introducing 1,2‐OD segments. The results of TGA and dynamic rheological testing indicate that the thermal stability of neat PBS is improved with the addition of 1,2‐OD segments. The incorporation of 1,2‐OD segments has some effects on the rheological properties of PBS, such as complex viscosities (|η*|), storage modulus (G′), and loss modulus (G″). Tensile testing demonstrates that the elongation at break is improved significantly with increasing 1,2‐OD segments content, but without a notable decrease of tensile strength. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and properties of hydrophilic segmented block copolymers based on poly(ethylene oxide)‐ran‐poly(propylene oxide)

The present article discusses the synthesis and various properties of segmented block copolymers with random copolymer segments of poly(ethylene oxide) and poly(propylene oxide) (PEO‐r‐PPO) together with monodisperse amide segments. The PEO‐r‐PPO contained 25 wt % PPO units and the segment presented a molecular weight of 2500 g/mol. The synthesized copolymers were analyzed by differential scanning calorimetry, Fourier transform infra‐red spectroscopy, atomic force microscopy and dynamic mechanical thermal analysis. In addition, the hydrophilicity and the contact angles (CAs) were studied. The PEO‐r‐PPO segments displayed a single low glass transition temperature, as well as a low PEO crystallinity and melting temperature, which gave enhanced low‐temperature properties of the copolymer. The water absorption values remained high. In comparison to mixtures of PEO/PPO segments, the random dispersion of PPO units in the PEO segments was more effective in reducing the PEO crystallinity and melting temperature, without affecting the hydrophilicity. Increasing the polyether segment length with terephthalic groups from 2500 to 10,000 g/mol increased the hydrophilicity and the room temperature elasticity. Furthermore, the CAs were found to be low 22–39° and changed with the crosslink density. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci 117:1394–1404, 2010     

Synthesis,characterization and properties of biodegradable poly(butylene succinate)‐block‐poly(propylene glycol) segmented copolyesters

BACKGROUND: To obtain a biodegradable thermoplastic elastomer, a series of poly(ester‐ether)s based on poly(butylene succinate) (PBS) and poly(propylene glycol) (PPG), with various mass fractions and molecular weights of PPG, were synthesized through melt polycondensation. RESULTS: The copolyesters were characterized using ¹H NMR, gel permeation chromatography, differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis, mechanical testing and enzymatic degradation. The results indicated that poly(ester‐ether)s with high molecular weights were successfully synthesized. The composition of the copolyesters agreed very well with the feed ratio. With increasing content of the soft PPG segment, the glass transition temperature decreased gradually while the melting temperature, the crystallization temperature and the relative degree of crystallinity decreased. Mechanical testing demonstrated that the toughness of PBS was improved significantly. The elongation at break of the copolyesters was 2–5 times that of the original PBS. Most of the poly(ester‐ether) specimens were so flexible that they were not broken in Izod impact experiments. At the same time, the enzymatic degradation rate of PBS was enhanced. Also, the difference in molecular weight of PPG led to properties being changed to some extent among the copolyesters. CONCLUSION: The synthesized poly(ester‐ether)s having excellent flexibility and biodegradability extend the application of PBS into the areas where biodegradable thermoplastic elastomers are needed. Copyright © 2009 Society of Chemical Industry     

An NMR study on sequence distributions of block copolymers of poly(butylene terephthalate) and poly(tetramethylene glycol)

Summary The analytical methods to characterize the exact chemical composition and sequence distributions of block copolymers of poly(butylene terephthalate) and poly(tetramethylene glycol) (PBT/ PTMG) were reinvestigated by NMR spectroscopy. To obtain accurate information, the choice of the solvents, NMR experimental conditions, ¹H and ¹³C peak assignments and the methods of calculating various sequence parameters were closely examined. For phenol-d₆/tetrachloroethane(TCE) solutions of two copolymers having the hard segment (PBT) contents of 20 and 35wt.%, various sequence parameters were extracted from NMR spectra. In addition to that, we could accurately measure the actual number average molecular weight of PTMG segments within the copolymer by NMR. Measured average molecular weight of PTMG segments was used to calculate theoretical sequence distributions. The experimental and theoretical sequence parameters as well as chemical compositions were compared with each other. Received: 8 September 1998/Revised version: 31 March 1999/Accepted: 2 April 1999