Segmented polyether ester copolymers—A new generation of high performance thermoplastic elastomers

This paper reviews a series of high-melting thermoplastic polyether esters prepared by transesterification from dimethyl terephthalate, polytetramethylene ether glycol (MW 600–2000), and 1,4-butanediol. The resulting copolyesters exhibit a two-phase domain structure consisting of amorphous polyether ester soft segments and crystalline tetramethylene terephthalate hard segments. By proper selection of the relative amounts of soft and hard segments, polymers ranging from relatively soft elastomers to impact resistant elastoplastics may be obtained. The preparation, polymer structure as well as the physical and environmental properties of polyether esters are discussed. The combination of good melt flow properties, excellent melt stability, and rapid hardening rates permits the processing of these polymers by a wide variety of methods. The excellent processing characteristics in conjunction with the unusual physical and mechanical properties of segmented polyether esters has led to their wide acceptance.     

Copolymers based on poly(butylene terephthalate) and polycaprolactone‐block‐polydimethylsiloxane‐block‐polycaprolactone

A series of novel thermoplastic elastomers, based on poly(butylene terephthalate) (PBT) and polycaprolactone‐block‐polydimethylsiloxane‐block‐polycaprolactone (PCL‐PDMS‐PCL), with various mass fractions, were synthesized through melt polycondensation. In the synthesis of the poly(ester‐siloxane)s, the PCL blocks served as a compatibilizer for the non‐polar PDMS blocks and the polar comonomers dimethyl terephthalate and 1,4‐butanediol. The introduction of PCL‐PDMS‐PCL soft segments resulted in an improvement of the miscibility of the reaction mixture and therefore in higher molecular weight polymers. The content of hard PBT segments in the polymer chains was varied from 10 to 80 mass%. The degree of crystallinity of the poly(ester‐siloxane)s was determined using differential scanning calorimetry and wide‐angle X‐ray scattering. The introduction of PCL‐PDMS‐PCL soft segments into the polymer main chains reduced the crystallinity of the hard segments and altered related properties such as melting temperature and storage modulus, and also modified the surface properties. The thermal stability of the poly(ester‐siloxane)s was higher than that of the PBT homopolymer. The inclusion of the siloxane prepolymer with terminal PCL into the macromolecular chains increased the molecular weight of the copolymers, the homogeneity of the samples in terms of composition and structure and the thermal stability. It also resulted in mechanical properties which could be tailored. Copyright © 2010 Society of Chemical Industry     

The thermal analyses of polymers. II. Thermomechanical analyses of segmented polyurethane elastomers

The development of new and more sensitive techniques in thermal analyses aids in a more complete understanding of the contributions of individual components in urethane elastomers regarding their mechanical and thermodynamic behavior. The behavior of various segments of the elastomers reported in this work illustrates a clearer interpretation of reasons for changes in mechanical behavior caused by changes in heat capacity, volume and tensile properties; the gross changes previously reported for polyurethane properties as a function of temperature are also confirmed with a more exact definition of their origin. The sub-ambient temperature behavior and response of physical measurements near the melting point of the backbone polyol are largely a function of the so-called “soft block.” The soft block does not contribute to the mechanical properties above the melting point of the polyol unless some urethane segments from the diisocyanate and extender are structured into the soft block, that is, excess diisocyanate and extender are added to build in the “hard” block. The extender and isocyanate influence for both low and high temperature properties is observed by the lack of molecular fit imparted to the backbone polyol as well as some crystallinity in the polymer hard block. The usual T_g transition reported in urethane elastomers corresponds to a first-order transition in the polyester or polyether backbone.     

Annealing-induced morphological changes in segmented elastomers

Thermal analysis has been used to study annealing-induced ordering in segmented elastomers. Twelve segmented elastomers were studied each having approximately 50% by wt hard segment content. Seven general classes of materials were examined including polyether and polyester polyurethanes, polyether polyurethane-urea, and polyether-polyester. Materials were slow cooled (?10°C min^?1) from the melt to an annealing temperature (?10°, 20°, 60°, 90° or 120°C) where they were annealed (16, 12, 8, 6 or 4 days, respectively). Annealing was followed by slow cooling (?10°C min^?1) to ?120°C after which a d.s.c. experiment was run. In general, annealing resulted in an endothermic peak at a temperature 20°–50°C above that of the temperature of annealing. This phenomenon was observed in both semicrystalline and amorphous materials. The closer the annealing endotherm was to a crystalline endotherm without exceeding it in temperature, the larger its size. Annealing endotherms resulted from hard or soft segment ordering. Only one annealing endotherm was observed for a given annealing history, even though in some materials hard and soft segments could exhibit annealing-induced morphological changes. Hard segment homopolymers were studied yielding results similar to the block polymers containing shorter sequences of the same material. This suggests that annealing-induced ordering is an intradomain phenomenon not associated with the interphase between domains, or necessarily dependent on the chain architecture of segmented elastomers.     

Thermostabile Polyester-Block-Copolymere

This paper describes the development of segmented thermoplastic polyester elastomers exhibiting superior heat aging characteristics. The most important members of this polymer class are the polyether esters which are obtained by transesterification of dimethyl terephthalate, poly(tetramethylene oxide glycol) (mol. wt. 1 000) and 1,4-butanediol. In spite of the poor oxidative stability of the aliphatic polyether segments, these copolymers can be effectively stabilized by the addition of suitable antioxidants, especially aromatic secondary amines. A significant improvement of the longterm thermostability of polyether esters is achieved by the additional use of costabilizers containing the . The latter prevent the formation of formic acid by functioning as scavengers for formaldehyde which is formed as an intermediate during the oxidative degradation. This reduces significantly chemical deactivation of the amine antioxidant by reaction with formic acid as well as acid-induced polymer cleavage. Novel thermoplastic polyester elastomers containing a branched C₃₆-hydrocarbon soft segment are obtained from dimer acid as starting material instead of poly(alkylene oxide glycol). The resulting copolyesters possess similar overall properties as the polyether esters, but exhibit much greater resistance toward oxidative degradation.     

The effect of segment length on some properties of thermoplastic poly(ester–siloxane)s

A series of novel thermoplastic elastomers, based on poly(dimethylsiloxane) (PDMS) as the soft segment and poly(butylene terephthalate) (PBT) as the hard segment, were synthesized by catalyzed two‐step, melt transesterification reactions of dimethyl terephthalate and methyl esters of carboxypropyl‐terminated poly(dimethylsiloxane)s (M?_n = 550–2170 g mol^?1) with 1,4‐butanediol. The lengths of both the hard and soft segments were varied while the weight ratio of the hard to soft segments in the reaction mixture was maintained constant (57/43). The molecular structure, composition and molecular weights of the poly(ester–siloxane)s were examined by ¹H NMR spectroscopy. The effectiveness of the incorporation of the methyl‐ester‐terminated poly(dimethylsiloxane)s into the copolymer chains was verified by chloroform extraction. The effect of the segment length on the transition temperatures (T_m and T_g) and the thermal and thermo‐oxidative degradation stability, as well as the degree of crystallinity and hardness properties of the synthesized TPESs, were studied. Copyright © 2003 Society of Chemical Industry     

Novel Segmented Thermoplastic Polyurethanes Elastomers Based on Tetrahydrofuran Ethylene Oxide Copolyethers as High Energetic Propellant Binders

Novel thermoplastic polyurethane (TPU) elastomers based on copolyether (tetrahydrofuran ethylene oxide) as soft segments, isophorone diisocyanate and 1,4‐butanediol as hard segments were synthesized for the purpose of using as propellant binders. In order to increase the miscibility of thermoplastic polyurethane elastomers with nitrate ester, polyethylene glycol (PEG) is incorporated in the co‐polyether (tetrahydrofuran ethylene oxide) as soft segment. When the molecular weight and content of polyethylene glycol are controlled to 4000 and 6% of soft segments, respectively, the properties of thermoplastic polyurethane elastomers are most perfect. If plasticizing ratio of nitrate ester to thermoplastic polyurethane elastomers exceeds 4 no crystallinities are determined at room temperature. The propellant samples were prepared by a conventional absorption‐rolling extrusion process and the mechanical and combustion properties evaluated afterwards. The maximum impulse reaches up to 265∼270 s which is a little bit higher than that of a HTPB propellant. The measured results reveal a promising TPE propellant candidate which shows good processing temperature (<393 K) and excellent mechanical properties. An attracting feature which can be pointed out is that the burning rate pressure exponent reaches as low as 0.36 without the addition of burning rate catalysts. This enables an easy control of propellant combustion.     

Structure property studies of polyester- and polyether-based MDI–BD segmented polyurethanes: Effect of one- vs. two-stage polymerization conditions

The effect of the polymerization method (one-or two-stage) on the morphology and properties of specific polyether- and polyester-based urethanes was studied. For the systems investigated, the polymerization technique was somewhat more influential on properties when the soft segment was a polyester than when it was a polyether. In the case of the polyester, a one-stage process yields materials with somewhat poorer physical properties than for a two-stage technique. This decrease in properties is attributed to a higher soft–hard segment interaction and to the higher mutual solubility of the segments that is brought about by a possible broader molecular weight distribution of hard segments produced in a one-stage reaction. A large difference in hard segment length distribution, however, was not expected since the MDI isocyanate moieties should display equal reactivity. In the case of polyether soft segments, any effect of the polymerization method appears to be largely offset by the higher incompatibility of the hard and soft components.     

Polyether‐based main‐chain‐type polytriazole elastomer with benzoxazine via a 1,3‐dipolar cycloaddition reaction

A novel functional polyether‐based elastomer with a benzoxazine structure in its main chain was successfully synthesized via a 1,3‐dipolar cycloaddition reaction. Benefitting from a facile one‐pot synthesis strategy, the elastomer was prepared at low temperature (80°C) and was characterized clearly afterward. The azide‐terminated polyether and acetylene‐terminated benzoxazine were used as the soft and hard segments, respectively, in the polymer chain. Because the triazole rings served as stable linkage between the soft and hard segments, the elastomer possessed good thermal stability (the 5% weight loss temperature could exceed 350°C) compared to traditional elastomers, such as polyurethane. The rigid benzoxazine rings provided the product with good mechanical properties (the tensile strength of the elastomer could exceed 30 MPa). Furthermore, the ring‐opening polymerization of oxazine rings in the structure gifted the elastomer with possibility of thermally induced structural transformation. The thermally induced structural transformation could conveniently realize the conversion of the elastomer to a thermosetting resin. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 132, 42820.     

Effects of co‐hard segments on the microstructure and properties thermoplastic poly(ether ester) elastomers

A thermoplastic poly(ether ester) elastomer (TPEE) is composed of polyester hard segments and polyether soft segments. Polyester and polyether segments are often homopolymer segments. This work aims at incorporating poly(butylene phthalate (PBP) as co‐hard segments in the hard segments of poly(butylene terephthalate) (PBT)‐b‐poly(tetramethylene oxide) (PTMO) thermoplastic elastomer, and investigating structures and properties of the resulting materials, denoted as (PBT‐co‐PBP)‐b‐PTMO. (PBT‐co‐PBP)‐b‐PTMO was synthesized from dimethyl terephthalate (DMT), dimethyl phthalate (DMP), PTMO (M_n = 1000 g/mol), and 1,4‐butanediol (BDO). The crystallinity of (PBT‐co‐PBP)‐b‐PTMO first decreased and then increased with increasing PBP content from 5% to 10% due to a decrease in the average sequence length of the PBT hard segments. Its elongation at break was increased by 200–350%. When the mass fractions of PBT and PBP were 42% and 8%, respectively, the (PBT‐co‐PBP)‐b‐PTMO showed the best performance in terms of permanent deformation, strength, and hardness whose values were 30%, 25 MPa, and 37 D, respectively. All the synthesized copolymers had good thermal stability with a decomposition temperature of 400°C or so. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43337.     

Blends of Bio-Based Poly(Limonene Carbonate) with Commodity Polymers

In this study, blends of the bio-based poly(limonene carbonate) (PLimC) with different commodity polymers are investigated in order to explore the potential of PLimC toward generating more sustainable polymer materials by reducing the amount of petro- or food-based polymers. PLimC is employed as minority component in the blends. Next to the morphology and thermal properties of the blends the impact of PLimC on the mechanical properties of the matrix polymers is studied. The interplay of incompatibility and zero-shear melt viscosity contrast determines the blend morphology, leading for all blends to a dispersed droplet morphology for PLimC. Blends with polymers of similar structure to PLimC (i.e., aliphatic/aromatic polyester) show the best performance with respect to mechanical properties, whereas blends with polystyrene or poly(methyl methacrylate) are too brittle and polyamide 12 blends show very low elongations at break. In blends with Ecoflex (poly(butylene adipate-co-terephthalate)) and Arnitel EM400 (copoly(ether ester)) with poly(butylene terephthalate) hard and polytetrahydrofuran soft segments) a threefold increase in E-modulus can be achieved, while keeping the elongation at break at reasonable high values of ≈200%, making these blends highly interesting for applications.     

不同原料对合成PUR弹性体性能的影响

采用相同官能度、不同分子量的聚醚多元醇和甲苯二异氰酸酯(TD I)及扩链剂反应合成了系列聚氨酯(PUR)弹性体,同时对所合成的PUR弹性体进行了表征。结果表明,聚醚多元醇的相对分子质量对PUR弹性体的性能有较大影响,相对分子质量越大,柔性链段含量就越多,弹性体的拉伸强度、断裂强度和硬度就减小,断裂伸长率则相对提高。同时也进一步证明了软硬链段之间的均匀分布和较强的相互作用更有利于弹性体力学性能的提高。     

Correlations between chemical structure,stress-induced crystallization,and deformation behavior of polyurethane elastomers

The deformation behavior of polyurethane elastomers depends strongly on physical interactions. In this paper the stress-induced crystallization of the polyester or polyether segments in investigated in several polyurethane elastomer systems having different chemical structure for the soft segments. The correlation between the tensile properties (hysteresis loss, extension set, modulus) and the stress-induced crystallization is discussed.     

Biconstituent fibers from segmented polyurethanes and nylon 6

The characteristics of Monvelle, a new biconstituent fiber from nylon 6 and a segmented polyurethane, are reviewed briefly, and some of the technical problems inherent in producing such a fiber are discussed. The characterization of two series of polyurethanes which can be melt spun is given in detail. The chemical composition of the hard segment was maintained constant, being derived from 4,4′-diphenylmethane diisocyanate (MDI) and 1,4-butanediol, in all polymers. In one series using poly(butylene adipate) of MW 2000 as the soft segment, the average hard segment content was varied from 33% to 54%. In the other series, the hard segment content was held at 43%, and three additional soft segments, each at MW 2000, were used: poly(ethylene adipate), polycaprolactone and poly-1,4-oxybutylene glycol (PBG). Characterizations include molecular weight distributions, thermal analysis, rheological studies, and selected small-angle and wide-angle x-ray diffraction and polarized light microscopy. Crystallinity, melt viscosity, and activation energy of flow increased with increasing hardsegment content. Changes in the polyester soft segments had little effect on the properties studied, but with PBG the crystalline melting point of the polymer, without annealing, was higher and the melt viscosity was slightly higher than corresponding polyester-based samples, in agreement with previous reports of sharper phase separation in polyether urethanes, compared to polyester urethanes.     

Mechanical,thermal, and electric properties of polyurethaneimide elastomers

Linear polyurethaneimide elastomers (PUI) were obtained from polyether- or polyester-diols, diphenylmethane diisocyanate or bitolylene diisocyanate and pyromellitic acid dianhydride. It was found that these polymers have considerably better mechanical properties than typical linear polyurethanes (PU). The elastic modulus and stress at break increase with contents of the hard polyimide segments. The softening temperatures and thermal stability of the PUI at 500°C were higher than the ones of PU with similar hard segment contents. Electric properties of PUI were close to the ones of conventional PU. It was shown that cellular PUI had considerably lower dielectric constant. T_g's of the soft segments PUI were less than T_g's corresponding to PU. It is connected with greater phase separation of the hard imide segments from the soft polyether– or polyester–urethane matrix.     

Tri-block copolymers with mono-disperse crystallizable diamide segments: Synthesis, analysis and rheological properties

Tri-block copolymers with polyether mid-segments and mono-disperse amide end segments were synthesized, analyzed and some properties studied. The end segment was an aromatic diamide (diaramide, TΦB). The polyether mid-segment was a difunctional poly(tetramethylene oxide) (PTMO, 1000 and 2900 g/mol). In order to increase the soft segment (SS) length, PTMOs were extended with terephthalic groups. The length of the mid-soft segment was varied from 1000 to 20,000 and thereby the concentration of the hard end segment changed from 22 to 3 wt.%. The molecular weight of the tri-block copolymers was determined by NMR and inherent viscosity measurements. The crystallinity of the hard segment was studied by IR and DSC measurements. Temperature modulated IR was carried out to explore the change in crystallinity with temperature. The morphology was investigated by AFM analysis and the thermo-mechanical properties by DMA, whereas the melt rheological behaviour was analyzed by a plate–plate method. The results of the tri-block copolymer were compared with those of a similar multi-block copolymer. The glass transition of the soft phase was low and the melting temperature of the diamide end blocks was high. The crystallinity of the hard end segments in the tri-block was found to be very high (>95%) and remained high until melting. The AFM picture showed crystalline ribbons with a high aspect ratio. Also the modulus at room temperature was relatively high, particularly at low contents of hard end segment. The melt rheological behaviour of a low molecular weight tri-block copolymer revealed a low melt viscosity at high shear rates, and a high viscosity at low shear rates. Moreover, a gelling of the melt was observed with decreasing frequency and this was probably due to agglomeration of the end segments.     

Dynamic mechanical properties of polyurethane block polymers

The dynamic mechanical properties of polyester and polyether urethane block polymers have been investigated at four frequencies (3.5, 11, 35 and 110 Hz) in the temperature range of — 150 to 200°C. The existence of a two phase structure was demonstrated in these systems by the observation of two major transition regions corresponding to (1) the glass transition temperature (T_g) of the ester or ether soft segments, and to (2) the softening temperature of the aromatic-urethane hard segments. Several secondary relaxations were observed in addition to the two major relaxations. It was possible to assign molecular mechanisms to each of these relaxations. All relaxation phenomena were greatly influenced by the molecular weight of the prepolymer, weight percent of hard segments, and thermal history. An increase in the molecular weight of the prepolymer above 1,000 at constant hard segment content resulted in a semi-crystalline material, which possessed a lower T_g for the macroglycol segments. Annealing to enhance crystallinity increased the T_g of the soft segments, consistent with the usual observation in semicrystalline homopolymers. These findings suggest that the relaxation mechanisms of polyurethane block polymers are not only influenced by the degree of crystallinity, but also by the nature of the domain structure.     

Effect of thermal history on properties of block-copolyetheresters with poly(tetramethylene 2,6-naphthalenedicarboxylate) segments

The effect of compression molding on the thermal transitions and crystalline properties of block-copolyetheresters with hard segments of poly(tetramethylene 2,6-naphthalenedicarboxylate) and soft segments of poly(tetramethylene oxide) were investigated by differential scanning calorimetry (DSC), X-ray diffraction, thermal stimulated current (TSC), and dynamic mechanical analysis (DMA). The X-ray diffraction patterns of compression molded samples of the block-copolymers were considerably different from those of the corresponding samples with slow-cooling history. After compression molding, the diffraction peaks were changed completely indicating a different crystalline structure for the polyester segments, and the diffraction peaks became sharper indicating a higher crystallinity. The DSC results also showed that the melting point and crystallinity of the polyester segments were increased after compression molding. The glass transition temperatures of the polyether soft phase and polyester hard phase also were determined by DSC, TSC, and DMA separately with consistent data and were found to be dependent on the content of polyether segments and the molecular weight of the poly(tetramethylene ether)glycol (PTMEG) used. A γ-transition was observed by TSC and DMA and seemed to be independent of the composition and the thermal history. The glass transition temperatures of the polyether soft phase and the polyester hard phase of the block-copolymers derived from PTMEG 650 and PTMEG 1000 shifted to a lower temperature after compression molding possibly because of the partial miscibility between the comprising segments in these two series. The abrupt drop in log G′ in the temperature range of −10–15°C for the block-copolymers derived from PTMEG 2000 was caused by the melting of the polyether segments and indicated that the crystalline properties of the polyether segments could affect their mechanical properties. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1441–1449, 1999     

The effect of soft‐segment structure on the properties of novel thermoplastic polyurethane elastomers based on an unconventional chain extender

Thermoplastic polyurethane elastomers (TPUs) are now widely used because of their excellent properties that include high tensile and tear strength, and good abrasion, impact and chemical resistance. TPUs are multiblock copolymers with alternating sequences of hard segments composed of diisocyanates and simple diols (chain extenders) and soft segments formed by polymer diols. Commonly used hard segments for TPUs are derived from 4,4′‐diphenylmethane diisocyanate (MDI) and aliphatic diols. The aim of our research was to examine the possibility of obtaining TPUs with good tensile properties and thermal stability by using an unconventional aliphatic‐aromatic chain extender, containing sulfide linkages. Three series of novel TPUs were synthesized by melt polymerization from poly(oxytetramethylene) diol, poly(ε‐caprolactone) diol or poly(hexane‐1,6‐diyl carbonate) diol of number‐average molecular weight of 2000 g mol^?1 as soft segments, MDI and 3,3′‐[methylenebis(1,4‐phenylenemethylenethio)]dipropan‐1‐ol as a chain extender. The structure and basic properties of the polymers were examined using Fourier transfer infrared spectroscopy, X‐ray diffraction, atomic force microscopy, differential scanning calorimetry, thermogravimetric analysis, Shore hardness and tensile tests. It is possible to synthesize TPUs from the aliphatic‐aromatic chain extender with good tensile properties (strength up to 42.6 MPa and elongation at break up to 750%) and thermal stability. Because the structure of the newly obtained TPUs incorporates sulfur atoms, the TPUs can exhibit improved antibacterial activity and adhesive properties. Copyright © 2011 Society of Chemical Industry