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New multiblock poly(ether-ester)s based on poly(trimethylene terephthalate) as rigid segments
A. Szymczyk, E. Senderek, J. Nastalczyk and Z. Roslaniec
Institute of Physics, Szczecin University of Technology, Al. Piastów 48, 70-310 Szczecin, Poland
Institute of Materials Science and Engineering, Szczecin University of Technology, Al. Piastów 19, 70-310 Szczecin, Poland
Received 4 June 2007; revised 18 October 2007; accepted 13 November 2007. Available online 21 November 2007.
Abstract
A series of novel poly(trimethylene terephthalate)-block-poly(tetramethylene oxide) (PTT--PTMO) segmented block copolymers were synthesised by transesterification in the melt of dimethyl terephthalate, 1,3-propanediol and poly(tetramethylene oxide) glycol (PTMO, 1000 g/mol). A range of multiblock copolymers were synthesized, with flexible PTMO segments contents varying from 20 to 80 wt%. The novel poly(ether-block-ester)s were characterized by using viscometry, hardness measurements, differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), and tensile properties.
Keywords:Poly(trimethylene terephthalate); Segmented block copolymers; Polyester thermoplastic elastomers
Introduction
Intensive study have been done on multiblock poly(ether-ester) (PEE) based on poly(butylene terephthalate) (PBT) as rigid segments and low molecular weight polyether flexible segments poly(tetramethylene oxide) (PTMO) [1], [2], [3] and [4]. The PBT-block-PTMO copolymers are of special interest due to their excellent mechanical properties, like strength and elastic properties in a wide temperature range. They are available as commercial products (ElitelTM, Elana; Arnitel, Hytrel®, Du Pont; DSM, etc.) [1]. In polyester thermoplastic elastomers many chemical modifications and also totally different chemical structure of polyester rigid segments have been examined and applied. In addition to PBT [1], [2], [3] and [4], poly(butylene-co-isophthalate) [5], PBT copolymers with unsaturated alkylene dicarboxylates or unsaturated glycols [6] and [7], poly(ethylene terephthalate) (PET) [4] and [8], poly(butylene 2,6-naphthalene dicarboxylate) [9] and [10], d,l-lactide [11], as well as other copolyesters with liquid crystalline or ionic units [12] and [13], aromatic polycarbonate [5] and [14] are used as rigid segments.
Poly(trimethylene terephthalate) (PTT) is newly commercialized aromatic polyester, which has become one of the most important polymer materials recently. PTT, with three methylene units in its glycol moiety, is called odd-numbered polyester. It is often compared to the even-numbered polyesters such as PET and PBT for the odd–even effect on their properties. It is well known that, in many polycondensation polymers, an odd or even number of methylene units in their chemical structure can affect physical properties of the polymers, so-called the odd–even effect. In fact, the elastic recovery is in an order of PTT > PBT > PET [15]. Many PET, PTT and PBT properties do not follow the odd–even effect and are additive and could be estimated by group contribution methods, such density and heat of fusion tend to follow the order of PET, PTT and PBT [16].
Since its commercialization in 1998, many studies based on PTT synthetic technique, spinning technology, morphological structure and properties of fiber, as well as crystallization behaviours have been widely investigated [14], [15], [16], [17], [18], [19] and [20]. PTT can also be used as an engineering thermoplastic because it possesses good thermal and mechanical properties [16] and [21]. Some of research work about structure and properties of multicomponent polymeric material, like poly(ethylene naphthalate), poly(ether imide), polystyrene, poly(ethylene terephthalate), and polycarbonate blending, with PTT were reported [22], [23], [24], [25] and [26]. There are no data concerning the incorporation of polyether flexible segments in PTT-based copolyesters in literature. Only a US Patent [27] describe the synthesis of PTT based polyether-ester elastomers comprising polytrimethylene ether-ester flexible segment and tetramethylene ester rigid segment.
In this paper we have synthesised poly(trimethylene terephthalate-block-tetramethylene oxide) (PTT–PTMO) copolymers. These type segmented copolymers based on PTT rigid segments and polyether flexible segments are expected to possess excellent thermoplastic elastomer properties, such as a low-temperature glass transition (Tg), a high melting point (Tm) and a temperature independent rubbery plateau. The influence of flexible segment content on the resulting PTT-b-PTMO copolymers properties, such thermal and mechanical properties was investigated.
Experimental Part
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Results and Discussion
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Conclusions
We have shown for the first time that the poly(ether-ester)s based on PTT as rigid segments and PTMOT as flexible segments, synthesized by conventional two-step melt polycondensation, can behave good thermoplastic elastomers properties. The synthesised PTT–PTMO copolymers exhibit low glass transition temperatures combined with high PTT melting temperatures even at high flexible segments contents, making these polymers suitable for low and high temperature range applications. The extensive relative elongation at break, the high elasticity, and low hardness (51–28 Sh D) of PTT–PTMO copolymers containing 50–80 wt% of PTMO segments are characteristic for poly(ether-ester) elastomers. By varying the flexible segments content, the mechanical properties such tensile modulus, elongation at break, can be adjusted to product requirements.
Further investigations on elastic properties and morphology depending on the composition and the length of soft segments are in progress and will be published elsewhere.
Acknowledgments
This work is sponsored by Polish Ministry of Science and High Education in years: 2007–2009. The authors would like to thank Shell Chemicals Company for supply 1,3-propanenediol used in synthesis of PTT–PTMO copolymers.
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European Polymer Journal
Volume 44, Issue 2, February 2008, Pages 436-443
Uwaga: Pełny tekst artykułu oraz teksty artykułów cytowanych są dostępne wyłącznie z komputerów zainstalowanych na serwerze Politechniki Szczecińskiej lub z komputerów dostępnych w czytelniach Wydziałowych Politechniki Szczecińskiej
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