Structure and Morphology Orientation of Comb-like Polymers with Rigid Backbones

V. Danke1,2, G. Gupta1,2, and M. Beiner1,2

1Fraunhofer-Institut für Mikrostruktur von Werkstoffen und Systemen IMWS, Walter-Hülse-Straße 1, 06120, Halle, Germany
2Institut für Chemie, Martin Luther Universität Halle-Wittenberg, 06120, Halle, Germany

Comb-like polymers with rigid backbones and flexible side chains are an important class of functional materials with applications in various fields like organic semiconductors and light weight components in high performance composite materials. A common feature of such polymers is the formation of layered structures with typical spacing in the 1-3 nm range wherein the side chains (long methylene sequences) aggregate to form alkyl nanodomains [1]. Crystallographic analysis in poly (1,4-phenylene-2,5-n-didecyloxy terephthalate) (PPDOT) and poly (2,5-didecyloxy-1,4-phenylene vinylene) (DOPPV) each having 10 alkyl carbons per side chain shows that PPDOT exhibits an orthorhombic unit cell, whereas the DOPPV is characterized by a monoclinic unit cell. The interplay between backbone and side chain packing within the alkyl nanodomain leading to different crystallographic states is discussed. Investigations on molecular orientation in extruded fibers of poly (1,4-phenylene-2,5-n-dialkyloxy terephthalate)s (PPAOT) and poly (2,5-dialkyloxy-1,4-phenylene vinylene)s (AOPPV) show that the backbones in case of PPAOT align along the shear direction whereas in AOPPV they align preferentially perpendicular to the shear direction [2]. Potential reasons for the differences in the preferred orientations for PPAOT and AOPPV are considered.

[1] About different packing states of alkyl groups in comb-like polymers with rigid backbones. T. Babur, G. Gupta and M. Beiner, Soft Matter, 2016, 12, 8093-8097 (link)
[2] Interrelations Between Side Chain and Main Chain Packing in Different Crystal Modifications of Alkoxylated Polyesters. G. Gupta, V. Danke, T. Babur, and M. Beiner. J. Phys. Chem. B, 2017, 121, 4583-45. (link)

Transition from Ring- to Chain-Dominated Phases in Supramolecular Polymer Networks

E. Lee, T. Shakirov, and W. Paul

Institut für Physik, Martin-Luther Universität Halle-Wittenberg, 06099 Halle (Saale), Germany

Rheological properties of supramolecular polymers depend on their structures including the size, the number, and the topology of aggregates. A linear polymer with hydrogen bonding units at both ends is one of widely used precursors to build the supramolecular polymer networks. Due to complex interplay between chain stiffness, hydrogen bonding interaction, and polymer conformational entropy it is difficult to theoretically predict the structure of the supramolecular polymer. In this work, we investigate structures of supramolecular polyethylene glycol and polybutylene glycols whose ends are capable of the hydrogen bond using a coarse-grained (CG) model via stochastic approximation Monte Carlo simulation (SAMC) method. Our CG force field is constructed by Boltzmann inversion of the probability distributions of all-atom polymer conformations. SAMC provides all the thermodynamic information of the system, which allows one to investigate supramolecular structures in a wide temperature range. This work especially focuses on the transition from ring- to chain-dominated phases since the contaminant of rings in a melt is known to significantly influence its rheology. In a limit of dilute concentration, the transition temperature (T*) shows non-monotonous behavior as molecular weight of the precursor increases due to competition between chain stiffness and hydrogen bonding. We also investigate the polymer concentration (c) dependence on T* to construct a c-T phase diagram.

Morphology–Density Relations in Polyamide 12

O. Verkinderen1, P. Adriaensens2, P. Van Puyvelde3 and B. Goderis1

1Polymer Chemistry and Materials, KU Leuven, Heverlee, Belgium
2Applied and Analytical Chemistry, UHasselt, Diepenbeek, Belgium
3Soft Matter, Rheology and Technology, KU Leuven, Heverlee, Belgium

A two-phase model consisting of alternating amorphous and crystalline layers is often used to describe the morphology of semi-crystalline polymers. However, this simple model – at least in the case of polyamide 12 (PA12) – does not allow rationalizing the outcome of different techniques which are sensitive to particular features of the semicrystalline morphology. Therefore, several authors argued for the existence of a third phase [1], [2]. This third phase is the rigid amorphous fraction (RAF) and is in fact a phase with a higher density and lower mobility than the amorphous fraction but without the order of the crystalline. Although the existence of this RAF seems beyond dispute, there clearly is no consensus on its topology. Based on a combination of temperature dependent WAXD, SAXS, solid state NMR, and density measurements a new morphological model is proposed for PA12, which consists of alternating solid and mobile (liquid) amorphous layers. The solid layers are in turn composed of crystalline and rigid amorphous patches with the density of the latter being intermediate between that of mobile amorphous and crystalline matter. This morphology, which includes a clear picture of the RAF topology, leads to a similarity in the WAXD and SAXS based crystallinity as well as to matching SAXS based dense and NMR based rigid fractions. The model adequately describes the SAXS patterns and produces overall densities that are identical to experimentally observed ones.

[1] B. Goderis, P. G. Klein, S. P. Hill, and C. E. Koning, Prog. colloid Polym. Sci., 130, 40 (2005). (link)
[2] C. Hedesiu, D. E. Demco, R. Kleppinger, G. Vanden Poel, W. Gijsbers, B. Blümich, K. Remerie, and V. M. Litvinov, Macromolecules, 40, no. 11, 3977 (2007). (link)

Synthesis, aggregation and crystallization of precision polymers with repetitive folding elements

M. B. Canalp, J. Freudenberg, S. Reimann and W. H. Binder

Martin Luther University Halle-Wittenberg, Faculty of Natural Sciences II, Chair of Macromolecular Chemistry, Von-Danckelmann-Platz 4, D-06120 Halle

The investigation of ordering phenomena in biological and synthetic macromolecules still presents an interesting and promising field of research. Biological macromolecules form stable secondary or higher structures via inter- and intramolecular ordering processes, which are based on the interaction of their precisely placed amino-acids and the rotational constraints resulting from the peptide bonds. [1] Especially the understanding of the secondary structure formation from polypeptides is essential as it depends strongly on their (bio)chemical environment.
We investigate the aggregation and crystallization behavior of different precision polymers, which are characterized by repeating sequences of synthetic polyolefins and different biomimetic structure-elements. Constraints like 2,6-diaminopyridine and urea induce a conformational restriction while poly(amino acids) like poly-L-glutamic acid, poly-L-aspartic acid, poly-L-lysine and poly-L-leucine display a large conformational variability and dynamic α-helical-to-coil-transition. [2] All included moieties additionally interact with each other via supramolecular interactions influencing the crystallization behavior of the polyethylene chain. Therefore, acyclic diene metathesis (ADMET) polymerization was used to achieve a periodic incorporation of the constraint into the polymer backbone, resulting in precision polymers, which were analyzed via DSC and WAXS measurements. [3]

[1] C. B. H. Anfinsen, E., J. Biol. Chem. 1961, 236, 1361. (link)
[2] P. Novotná, M. Urbanová Vib. Spectrosc. 2013, 66, 1. (link)
[3] S. Reimann, U. Baumeister, W. H. Binder, Macromol. Chem. Phys. 2014, 215, 1963. (link)

Small polyethylene systems: On the ground state of single chains and few chain aggregates

T. Shakirov, W. Paul

Institut für Physik, Martin-Luther-Universität Halle-Wittenberg, D-06099 Halle (Saale), Germany

The phase behavior of polyethylene has been under investigation for the last six decades. Investigation of single-chain crystallization in solution is a technically difficult problem, because in molecular dynamics simulations as well as in experiments, it is not so easy to distinguish kinetic and thermodynamic effects on chain folding. The general picture, however, is, that single polyethylene chains in solution fold into lamellar crystals. We present results of a Stochastic Approximation Monte Carlo (SAMC) simulation, which gives a possibility to analyze thermodynamical equilibrium properties of a system. Our simulation study of relatively short polyethylene chains is based on a chemically realistic united atom model [1]. Simulational results for low-energy states of single chains of different lengths demonstrate a set of various ground-state configurations: from stretched and hairpin-like configurations of short chains to a helix-like structure reeled round one of the chain’s ends. Aggregates of a few short polyethylene chains exhibit another set of ground states, depending on chain length and number of aggregated chains. However, with increasing chain length, single chain and aggregate morphologies become more similar.

[1] W. Paul, D.Y. Yoon, and G.D. Smith, J. Chem. Phys. 103, (1995) 1702 – 1709. (link)

SAXS Study on Density Fluctuations in Crystallization Process of Poly(trimethylene terephthtalate)

T. Konishi1, D. Tadokoro1, Y. Kawahara1, K. Fukao2 and Y. Miyamoto2

1Graduate School of Human and Environmental Studies, Kyoto University, Kyoto 606-8501, Japan
2Department of Physics, Ritsumeikan University, Noji-Higashi 1-1-1, Kusatsu 525-8577, Japan

Polymer crystallization mechanism especially at large supercooling has not been fully understood yet. Kaji et al. found that the density fluctuations occur in the early stage of crystallization in poly(ethylene terephthalate). [1] Research on such a fluctuations have been done from both theoretical [2] and experimental [3] aspects. But an interpretation for the fluctuations has not been fully obtained. Recently the strong density fluctuations are reported in the early stage of glass-crystallization process for poly(trimethylene terephthalate) (PTT)[4]. In order to clarify the density fluctuations in PTT, we have studied the crystallization processes of PTT from the glass and the melt by small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD).
The density fluctuations of several hundred Å have been obtained in the SAXS results in the early stage of crystallization process both from the glass and the melt. The fluctuations appear simultaneously with the generation of the nodular crystals of several tens Å. From the results we conclude that the fluctuations is due to the nodular crystals heterogeneously aggregated in space.

[1] K. Kaji et al., Adv. Polym. Sci. 191, 187 (2005). (link)
[2] A. J. Ryan et al., Faraday Discuss. 112, 13 (1999). (link)
[3] P. D. Olmsted et al., Phys. Rev. Lett. 81, 373–376 (1998). (link)
[4] W.T. Chuang et al., Macromolecules 44, 1140 (2011). (link)

NMR investigations of dynamics in the different phases of semicrystalline polymers

M. Schäfer, R. Kurz, A. Seidlitz, T. Thurn-Albrecht and K. Saalwächter

Institut für Physik, Martin-Luther-Universität Halle-Wittenberg, D-06099 Halle (Saale), Germany

The melt-crystallized morphology of semicrystalline polymers strongly depends on the diverse dynamics in the amorphous and crystalline region. The connections between structure formation and dynamics of polymer chains are investigated with SAXS and NMR spectroscopy, respectively, comparing polymers with and without intracrystalline dynamics (crystal-mobile and crystal-fixed). Proton time-domain techniques enable the analysis of the phase components, the intracrystalline and the amorphous phase dynamics. The intracrystalline motion displays only a weak dependence on morphology [1]. SAXS results show, that the morphology of the crystal-fixed polymer, poly-ε-caprolactone (PCL), and the crystal-mobile polymer, polyethylene oxide (PEO), are qualitatively different [2]. The crystal thicknesses in PCL are well-defined, whereas in PEO a crystal reorganization process caused by the intracrystalline dynamics leads to a uniform amorphous region [2].
To investigate the impact of the crystalline growth and reorganization process on the morphology separately, polymers with slower intracrystalline mobility, e.g. polyoxymehtylene (POM), will be investigated. Further investigations address the relationship between morphology and entangled dynamics in the amorphous phase.

[1] R. Kurz, A. Achilles, W. Chen, M. Schäfer, A. Seidlitz, Y. Golitsyn, J.  Kressler, W. Paul, G. Hempel, T. Miyoshi, T. Thurn-Albrecht, and K. Saalwächter. Macromolecules 2017, 50, 3890-3902.  (link)
[2] A. Seidlitz. 2016. “Einfluss von Kristallisationskinetik und Dynamik im Kristall und in der Schmelze auf die Strukturbildung teilkristalliner Polymere.” Dissertation, Martin-Luther-Universtität Halle-Wittenberg.  (link)

The Decisive Role of Intra-Crystalline Chain Dynamics for the Morphology of Semicrystalline Polymers

M. Schulz, A. Seidlitz, R. Kurz, R. Bärenwald, K. Saalwächter and T. Thurn-Albrecht

Institute of Physics, Martin Luther University Halle-Wittenberg

A special feature of some semicrystalline polymers is the existence of the so-called αc-relaxation, caused by a translational motion of the chains in the crystal. Although it was recognized already early on that these crystal-mobile polymers generally have a higher crystallinity than crystal-fixed polymers [1], differences in the semicrystalline morphology have not been analyzed in detail and the relaxation process has not been taken into account in most crystallization models. Using an extended method for quantitative analysis of small angle x-ray scattering data [2] we here compare the structural characteristics for two model polymers, namely PEO (crystal-mobile) and PCL (crystal-fixed). PCL follows the expectations of classical crystallization theories. The crystal thickness is well defined and determined by the crystallization temperature Tc. In contrast, for PEO the amorphous thickness is better defined. We hypothesize that due to the αc-relaxation, the crystalline lamellae thicken directly behind the growth front until the amorphous regions reach a minimal thickness. This assumption is consistent with NMR experiments, which give the time scale of intra-crystalline dynamics [3] and which show that crystal reorganization takes place on the same time scale as crystal growth itself. In keeping with this model, crystal-mobile and crystal-fixed polymers exhibit a different melting behavior during heating. The crystallization of PCL leads to the formation of marginally stable crystallites which constantly reorganize during heating, while in PEO due to the presence of the αc-relaxation, much more stable (thickened) lamellar crystals form, which melt only at much higher temperatures.

[1] Boyd, R.H.; Polymer 26, 323 (1985) (link)
[2] Seidlitz, A. et al. in Polymer Morphology, Wiley (2016) (link)
[3] Kurz, R. et al.; Macromolecules 50 (10), 3890 (2017) (link)

Chain Tilt in the Crystalline Lamellae of Poly(ethylene oxide) Investigated by Mid-Chain Defects

Martin Pulst, Yury Golitsyn, Christian Schneemann, Paweł Ruda, Detlef Reichert, and Jörg Kressler

Faculty of Natural Sciences II, Martin Luther University Halle-Wittenberg, Von-Danckelmann-Platz 4, D-06120 Halle (Saale), Germany

While many traditional schematic models show the crystalline polymer chains aligned parallel to the lamella thickness Lc recent sophisticated studies on poly(ethylene) show that the crystalline polymer chains are tilted at an angle φ to the lamella thickness [1].
Here, we investigate the chain tilt of poly(ethylene oxide) (PEO) by the means of mid-chain defects using wide-angle X-ray scattering and solid state 13C MAS cross polarization NMR spectroscopy. At low temperatures, one polymer chain of PEO9-meta-PEO9 and PEO11-TR-PEO11 [2-4] containing a 1,3-disubstituted benzene and a 1,4-disubstituted 1,2,3-triazole defect in central position of the polymer chain, respectively, form crystals and the other PEO chain as well as the defect remain amorphous. The aromatic defects of these two polymers can be incorporated into the crystalline lamellae upon heating below Tm and the corresponding structure models confirm that the amorphous PEO chains exit the tilted lamellae at a preordained angle. Thus, the chain tilt angle φ can directly be calculated from the bent angle ξ between the amorphous and crystalline PEO chains, which is given by the substitution patterns of the aromatic mid-chain units and a tilt angle range between 36° ≤ φ ≤ 60° is determined. Furthermore, our studies on PEO9-para-PEO9 containing a 1,4-disubstituted benzene mid-chain defect confirm that also linear unbent PEO chains form tilted lamellae.

[1] K. J. Fritzsching, et al., Macromolecules 50, 1521-1540 (2017). (link)
[2] M. Pulst, et al., submitted (2017).
[3] M. Pulst, et al., Macromolecules 49, 6609-6620 (2016). (link)
[4] Y. Golitsyn, et al., J. Phys. Chem. B 121, 4620-4630 (2017). (link)

Dissection of elastomeric performances of ethylene based semicrystalline multi-block copolymers

F. Auriemma, C. De Rosa, M. Scoti, G. Talarico

Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Complesso Monte Sant’Angelo, via Cintia, 80126 Napoli.

The crystallization properties, morphology and elastomeric behavior of some ethylene/1-octene multi-block copolymers produced by chain shuttling technology [1] are analyzed. We evidence that the samples consist of a reactor blend of chains characterized by alternation of crystalline (hard) blocks with low octene content and amorphous (soft) blocks with high octene content, having different length and different number of blocks. The sample show similar degree of crystallinity and melting temperature, and good elastomeric properties at 25°C. Differences occur for the crystallization temperature, morphology and elastomeric properties at 60°C. These differences reflect differences in segregation strength. For samples containing a high fraction of chains with hard-blocks of short length, and long soft-blocks, the segregation strength is high, and the hard domains are well separated at high correlation distances. For samples containing a high fraction of chains characterized by long hard-blocks and short soft-blocks some kind of interpenetration of the hard segments in the soft domains occurs, with consequent decrease of segregation strength and interdomain distance. Since the long hard-segments can also connect different hard-domains, a well interpenetrated network is formed. Therefore, the samples forming an interpenetrating network crystallize at lower temperatures (more slowly), show high mechanical strength and ductility, and good elastomeric properties even at high temperatures. The samples with no inter-woven structure with short hard-blocks, instead, form a more heterogeneous morphology, show low mechanical strength and lose elastomeric properties already at 60°C.

[1] D.J. Arriola, E.M. Carnahan, P.D. Hustad, R.L. Kuhlman, T.T Wenzel, Science, 312, 714 (2006). (link)