The effect of chain packing on the thermal and dynamic mechanical behaviour of liquid-crystalline epoxy thermosets (original) (raw)
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Polymer Degradation and Stability, 2007
Thermal non-oxidative degradability of two epoxy thermosets was studied. Investigations were carried out on a non-commercial liquid crystalline structure and its isotropic homologue in order to provide further insight into the mechanism and kinetics of thermal degradation of the proposed systems. The studies were done by thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). For the first time the degradation of a liquid crystalline epoxy was studied using an advanced isoconversional kinetic method. The results were used to predict the thermal stability of both types of epoxy networks. GCeMS analysis was applied on evolved gas during degradation to elucidate the degradation mechanism in accordance with the kinetic results. The liquid crystalline structure has a different mechanism of decomposition in comparison with its isotropic homologue. In spite of a higher T g value, it shows a similar thermal stability but a lower release of degradation compounds.
Liquid crystal thermosets. A new class of high-performance materials
Liquid Crystals, 2019
The evolution of the liquid crystalline order during the cure of a reactive thermotropic liquid crystal (LC) is studied using two phenylethynyl-terminated biphenol and naphthalenediol model compounds. The nematic order in the melt of both model compounds at elevated temperature is monitored with X-ray Diffraction (XRD) and C-13 Nuclear Magnetic Resonance (13 C NMR). XRD shows a cybotactic nematic phase; the global nematic order decreases with curing and eventually the resulting cross-linked liquid crystal thermoset (LCT) exhibits an isotropic morphology. The NMR method tracks the phenylethynyl end-group and yields data about the cure kinetics of this class of reactive LC mesogens. The observations may be used to make inferences about the cure behaviour and morphology of phenylethynyl-terminated random copolyester macromonomers.
Journal of Polymer Science Part A: Polymer Chemistry, 2004
A new series of liquid-crystalline epoxy resins was synthesized, and their mesomorphic behavior was investigated with differential scanning calorimetry, polarized optical microscopy, and wide-angle X-ray scattering. These glycidylic compounds had central aromatic imine mesogens derived from benzidine and aliphatic spacers of up to 10 methylene units that linked the mesogens to the glycidylic groups. Crosslinking these monomers with primary aromatic diamines led to nematic networks, some of which contained crystal inclusions. However, through curing with tertiary amines as catalytic agents or through copolymerization with different proportions of the nonmesomorphic epoxy monomer and primary amines as crosslinking agents, smectic C organized thermosets were prepared when the spacers had at least four methylene carbons. When they had fewer than four, the networks were nematic.
Influence of cross-link density on the properties of ROMP thermosets
2009
A norbornene-based cross-linker was synthesized and mixed at different loadings with two separate monomers for self-healing polymer applications: 5-ethylidene-2-norbornene (ENB) and endo-dicyclopentadiene (endo-DCPD). The monomer/cross-linker systems were polymerized by ring-opening metathesis polymerization (ROMP) with Grubbs' catalyst. The thermal-mechanical properties of the polymerized networks were evaluated by dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) and the curing process was monitored by parallel plate oscillatory rheometry. The viscosities of the pre-polymer blends are shown to be adequately low for self-healing, and exhibit a high ROMP reactivity to form cross-linked networks with enhanced thermal-mechanical properties. The addition of cross-linker increases the glass transition temperature (T g ) and the storage modulus both above and below T g . The storage modulus increase above T g is used to estimate the molecular weight (M c ) between entanglements or cross-link sites for both ENB and endo-DCPD-based networks. The crosslinker also greatly accelerates network formation as defined by the gelation time.
Synthesis and curing of novel LC twin epoxy monomers for liquid crystal thermosets
1996
This article describes the synthesis and characterization of new liquid crystalline thermosets having a twin structure. Nematic epoxy-terminated monomers based on a phenyl benzoate twin mesogen connected by an alkylene spacer were synthesized for these studies. In addition, an epoxy-terminated monomer based on a 1,4-bis(benzoyloxy)phenylene mesogen was synthesized to determine the effect of the position of the mesogen on the final network structure. The diepoxy monomer made with phenyl benzoate twin mesogens connected with an alkylene spacer formed a smectic-like network when cured with diamines. This smectic organization appeared even though the diepoxy monomer itself showed only a nematic mesophase over a narrow temperature range. The presence of crosslinks at both ends of the mesogens helped to retain a uniform spacing between crosslinking sites during the curing reaction, and aided formation of the smectic layer arrangement. The epoxy monomer possessing a 1,4-bis(benzoyloxy)phenylene mesogen and two epoxidized alkylene end groups on both sides of the mesogen formed a stable nematic mesophase. However, in contrast to the twin epoxies, the latter epoxy when reacted with diamines tended to produce a nematiclike network which was retained as the crosslinking reaction proceeded.
Shear induced structuration of liquid crystalline epoxy thermosets
European Polymer Journal, 2010
Low-molecular weight liquid crystals (LC) have wide technological applications due to their self-assembly in the mesophase. An azomethine nematic monomer based on diglycidyl functionalized mesogenic core and without spacers has been cured with a diamine. The great affinity of LC epoxy to the formation of ordered structures introduces a spatial driving force into the process of curing. Thermal and LC behaviors were investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The nature of the LC phases was confirmed by X-ray diffraction. Rheological experiments were conducted during crosslinking at different shear stresses. The viscosity of the mixture is strongly decreasing by three orders of magnitude when the solid epoxy is melting into a LC phase, and is increasing again due to the curing. Unexpected results were found. Applying a stress during curing had a profound influence on the ordering of the structure. The material becomes isotropic if a small shear stress is applied. Then, the higher the stress is, more ordered the final material is. For the highest stresses, the final material is in a highly ordered, quasi-crystalline, smectic structure.X-ray patterns of structuration of E1/MCDEA LC thermoset cured under shear at 200 (a), 400 (b) and 600 Pa (c).
Macromolecular Chemistry and Physics, 1997
Lightly crosslinked liquid crystalline epoxy resins were synthesized by reacting rigid rod epoxy-terminated molecules with decanedioic acid (SA). The obtained networks exhibited a smectic phase even in the case of 2,6-bis(2,3-epoxypropoxy)naphthalene, whose aspect ratio is very low. Upon application of uniaxial stress, a smectic phase was surprisingly obtained also for the system obtained by reacting p-bis(2,3-epoxypropoxy)benzene (QH), whose aspect ratio is practically equal to one, and SA. Stretching of the smectic samples above the glass transition temperature determines orientation of polymer chains, yielding considerably high values of the order parameter S. Thermomechanical analysis showed, for one of these systems, that stretching induces a shift of the isotropization temperature to higher values.
Thermotropic liquid-crystalline polymers: A new type of mesomorphic macromolecular system
1980
A new approach to the synthesis of thermotropic liquid-crystalline (LC) polymers is described based on the polymerization of monomers containing various mesogenic groups attached to the backbone chain by flexible polymethylene spacer groups. Dozens of new LC polymers are described, including derivatives of polymethacryloyl L-lysine, cholesteric esters of long-chain aminocarboxylic acids, and other aromatic polymers. Phase transition temperatures, heats of fusion, and x-ray structural analysis were evaluated. Polymers exhibiting spontaneous optical anisotropy in the glasslike, elastic, and fluid states are described, and schemes of molecular packing in the LC phase are proposed. We show the possibility of realizing smectic, nematic, and cholesteric types of structures in these thermotropic LC polymers. A n LC structure for various comblike copolymers not having mesogenic groups at every monomeric unit was detected. The role of specific interactions in side groups and their mobility in allowing for the LC structure are discussed, and the necessity of having particular conformations of the macromolecules is shown to provide the LC structure in films made from various solutions.
Journal of Polymer Science Part A: Polymer Chemistry, 2003
We studied the curing processes of several series of dimeric liquid-crystalline epoxyimine monomers with 2,4-toluene diisocyanate (TDI) alone or with added catalytic proportions of 4-(N,N-dimethylamino)pyridine. We obtained isotropic materials or liquid-crystalline thermosets with different degrees of order, which depended on the structures of the monomers. To fix ordered networks, we had to do the curing in two steps when TDI was used alone as the curing agent. However, when a tertiary amine was added in catalytic proportions, the ordered networks were fixed in just one step. In this way, we were able to fix both nematic and smectic mesophases. The significance of the polarization of the mesogen for obtaining liquid-crystalline thermosets was demonstrated.