The cyclolinear polyorganosiloxanes - a new class of mesomorphic polymers

The paper summarizes the recent achievements concerning the influence of the chemical structure and rigidity of cyclolinear polyorganosiloxane chains on the glassy, crystalline and mesophase behaviour with a special emphasis on the temperature range of mesophase stability and some thermal, X-ray and optical characteristics of their mesophase state. The packing of macromolecules in the mesophase state is suggested.     

The effect of compatibilization and rheological properties of polystyrene and poly(dimethylsiloxane) on phase structure of polystyrene/poly(dimethylsiloxane) blends

The compatibilization effect of polystyrene (PS)‐poly(dimethylsiloxane) (PDMS) diblock copolymer (PS‐b‐PDMS) and the effect of rheological properties of PS and PDMS on phase structure of PS/PDMS blends were investigated using a selective extraction technique and scanning electron microscopy (SEM). The dual‐phase continuity of PS/PDMS blends takes place in a wide composition range. The formation and the onset of a cocontinuous phase structure largely depend on blend composition, viscosity ratio of the constituent components, and addition of diblock copolymers. The width of the concentration region of the cocontinuous structure is narrowed with increasing the viscosity ratio of the blends and in the presence of the small amount diblock copolymers. Quiescent annealing shifts the onset values of continuity. The experimental results are compared with the volume fraction of phase inversion calculated with various theoretical models, but none of the models can account quantitatively for the observed data. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 898–913, 2004     

29Si NMR study of configurations of cyclo-linear polymethylsiloxanes

A technique based on the²⁹Si NMR spectra for analyzing the spatial structure of cyclolinear polymethylsiloxanes has been developed. The role of certain factors influencing the formation of the spatial structure of the chains during the preparation of these polymers has been studied.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1460–1466, August, 1993.     

Studies on droplet size distributions during coalescence in immiscible polymer blends filled with silica nanoparticles

The effect of silica nanoparticles on the morphology of （10/90 wt%） PDMS/PBD blends during the shear induced coalescence of droplets of the minor phase at low shear rate was investigated systematically in situ by using an optical shear technique. Two blending procedures were used： silica nanoparticles were introduced to the blends by pre-blending silica particles first in PDMS dispersed phase （procedure 1） or in PBD matrix phase （procedure 2）. Bimodal or unimodal droplet size distributions were observed for the filled blends during coalescence, which depend not so much on the surface characteristics of silica but mainly on blending procedure. For pure （10/90 wt%） PDMS/PBD blend, the droplet size distribution exhibits bimodality during the early coalescence. When silica nanoparticles （hydrophobic and hydrophilic） were added to the blends with procedure l, bimodal droplet size distributions disappear and unimodal droplet size distributions can be maintained during coalescence; the shape of the different peaks is invariably Gaussian. Simultaneously, coalescence of the PDMS droplets was suppressed efficiently by the silica nanoparticles. It was proposed that with this blending procedure the nanoparticles should be mainly kinetically trapped at the interface or in the PDMS dispersed phase, which provides an efficient steric barrier against coalescence of the PDMS dispersed phase. However, bimodal droplet size distributions in the early stage of coalescence still occur when incorporating silica nanoparticles into the blends with procedure 2, and then coalescence of the PDMS droplets cannot be suppressed efficiently by the silica nanoparticles. It was proposed that with this blending protocol the nanoparticles should be mainly located in the PBD matrix phase, which leads to an inefficient steric barrier against coalescence of the PDMS dispersed phase; thus the morphology evolution in these filled blends is similar to that in pure blend and bimodal droplet size distributions can be observed during the early coalescence. These results imply that exploiting non-equilibrium processes by varying preparation protocol may provide an elegant route to regulate the temporal morphology of the filled blends during coalescence.     

Self-organizing silane-siloxane copolymers: Synthesis and behavior in the block and monomolecular layers

Trans tactic cyclolinear organosilicon copolymers with a regular alternation of decamethylcyclohexasiloxane and decamethylcyclosilane units have been synthesized by the heterofunctional polycondensation of trans-2,8-dihydroxydecamethylcyclohexasiloxane with 1,3-or 1,4-dichlorodecamethylcyclohexasilanes. The structure of the copolymers has been studied by ¹H and ²⁹Si NMR, and IR spectroscopy; molecular mass measurements; and elemental analysis. The phase behavior of these copolymers in the block has been examined by DSC, X-ray diffraction, and polarization optical microscopy. It has been demonstrated that the copolymers of interest may exist in the mesomorphic state within a wide temperature interval. The ability of cyclolinear organosilicon copolymers to spread at the water/air interface and to form monolayers has been investigated. It has been shown that cyclosilane units that are structural isomers affect the pattern of surface pressure isotherms of the said copolymers.     

Synthesis of cyclolinear polymethylsiloxanes with two reactive groups and liquid-crystalline polymers on their basis

Cyclolinear polymethylsiloxanes with reactive vinyl groups at the silicon atoms in the fragment SiO_3/2 have been synthesized for the first time by heterofunctional polycondensation of [2,6(2,8)-dichloro-2,6(2,8)-divinyl]methylcyclotetra(hexa)siloxanes with the corresponding dihydroxy derivatives. Their hydrosilylation with chlorodimethylsilane gives rise to cyclolinear polymers with 2-chlorodimethylsilylethyl substituents, hydrolysis of which leads to the corresponding hydroxy derivatives. Liquid-crystalline polymers with mesogenic cyanobiphenyl groups have been synthesized by hydrosilylation with (4’-cyanobiphenyl-4-yl) 11-(1, 1, 3, 3-tetramethyldisiloxanyl)undecanoate. The structures of the polymers obtained have been studied by ¹H and ²⁹Si NMR and IR spectroscopy, GPC, viscometry, X-ray diffraction, and polarization optical microscopy.     

Chiral nematic phase in hydrogen-bonded blends of a side-chain smectic polymer with low molar mass dopants

The possibility of chiral nematic mesophase induction in blends of a smectic A side-chain liquid-crystalline copolymer with low molar mass dopants was studied. The chirality of the initial copolymer was determined by the cholesterol optical active groups; however, in the individual state it was not able to form any chiral liquid-crystalline phases. We have shown that the induction of the chiral nematic phase becomes possible in blends of such a copolymer with low molar mass dopants that are stabilized by hydrogen bonding. Phase behavior and optical properties of the blends were studied with X-ray scattering, differential scanning calorimetry and polarizing microscopy. Owing to hydrogen bonding the blends are stable over a wide range of contents and temperatures. The nature of the end group in the dopant molecules is shown to have an important influence on the chiral mesophase induction concentration and the clearing temperatures of the blends. Temperature and concentration dependences of the selective reflection maximum wavelength in the chiral nematic phase were also studied.

Transient interfacial tension and morphology evolution in partially miscible polymer blends

The influence of molecular weight asymmetry across an interface on the transient behavior of the interfacial tension is investigated for two different polymer combinations, polybutadiene (PBD)/polydimethylsiloxane (PDMS) and polybutene (PB)/PDMS. This choice ensures a minor diffuse interface using the first combination and a very diffuse interface in the latter case. Measurements of the interfacial tension as a function of time are carried out using a pendent/sessile drop apparatus at different temperatures ranging from 0 degrees C to 80 degrees C. Variations in the transient interfacial tension are attributed to diffusion of the lower molecular weight components from one phase into the other and the most pronounced changes are measured for the most diffusive systems (low molecular weight and high polydispersity) when diffusion goes from the drop into the matrix. By reversing the phases, only minor changes in the transient interfacial tension are measured. This is due to a fast saturation of the drop-phase since the drop volume is much smaller than that of the continuous phase. In all cases investigated, after a sufficient time a steady value of the interfacial tension is reached. In order to estimate the characteristic diffusion times of the migrating species, a discrete solution of the diffusion equation and a kinetic model from literature are applied. Results obtained are in line with the experimental observations. The importance of a changing interfacial tension on morphology development is studied on dilute (1%) blends, using two in situ techniques: small angle light scattering (SALS) and optical microscopy (OM). The SALS patterns yield the time evolution of the drop size, which is subsequently compared with the morphology following from OM. Depending on the diffusivity of the system, the morphology development is dominated by either diffusion or coalescence. Existing sharp-interface drainage models indeed do not apply for the diffuse blends and an improved quantitative estimation of the value of the critical film thickness is needed.     

Formation of columnar mesophases by calamitic molecules: a modulated SmA phase in mixtures of amphiphilic and bolaamphiphilic biphenyl derivatives

Binary mixtures of bolaamphiphilic biphenyl derivatives with each other and with amphiphilic biphenyl derivatives were investigated by means of optical microscopy. The miscibility of the bolaamphiphiles is very sensitive to the molecular length of the components. The SmA phases of bolaamphiphiles with the same length are completely miscible. If the length difference between the two components of the binary system increases, a miscibility gap occurs. Due to their different phase structures (bilayer versus monolayer) no miscibility in the SmA phases was found for amphiphilic and bolaamphiphilic compounds with comparable molecular lengths. However, in some cases a novel mesophase was induced in the contact region. This mesophase was investigated by X-ray diffraction. It represents a two-dimensionally modulated (columnar) phase with a rectangular lattice (Col r), but the local order is similar to that of disordered smectics. Its formation is explained in terms of ribbon structures resulting from the collapse of smectic bilayers, in strong analogy to the antiphases (SmA) of terminally polar calamitic mesogens.     

Condis-crystal structure of flexible-chain polymers in polymer blends

When heated above the melting point, a thermodynamic equilibrium mesophase of conformationally disordered crystal type (so-called condis state) has been found in some flexible-chain polymers (not containing mesogenic groups) dispersed in a matrix of another polymer. Typical organic and inorganic polymers such as polyethylene (PE) and poly[bis (2, 2, 2-trifluoroethoxy) phosphazene] (PPh) were taken as main components of the polymer blends under investigation. The most interesting situation is realized if two mesophase polymers are used in the same binary blend.     

Structural evolution of liquid-crystalline solutions of hydroxypropyl cellulose and hydroxypropyl cellulose-based nanocomposites during flow

The phase state and orientation and dissipative characteristics of biphasic LC HPC-water solutions and filled systems formed on their basis during shear flow are studied by various methods. The concentration of solutions is selected on the basis of the corrected phase diagram constructed with the use of optical interferometry. Flow curves and concentration dependences of viscosity provide additional information about the phase state and structure of the samples and the role of fillers in the rheological properties of solutions. X-ray diffraction data are obtained with the use of a Couette cell consisting of two coaxial capillaries. In the case of a clay suspension in water, practically no orientation is attained. However, in the isotropic 30% solution, clay particles easily orient, a result that indicates an important role of the viscoelasticity of a medium in the orientation process. The development of orientation of HPC macromolecules and clay particles in relation to the shear rate is analyzed separately for systems with the biphasic matrix (LC + isotropic phase). In addition, the time decay of the orientation parameter during relaxation is investigated. It is shown that higher shear rates cause a more rapid relaxation of orientation, for which recovery of the cholesteric helix typical for LC solutions of cellulose derivatives in the equilibrium state plays an important role. Order parameters (separately for the two components) are calculated, and their evolution with the shear rate and total deformation is investigated for systems containing clay nanoparticles (also the structure-active component) in LC solutions. On the basis of these data, it is hypothesized that clay particles form the columnar mesophase, which, under certain conditions, may transform into the discotic mesophase. This transition is responsible for a certain decrease in the order parameter of HPC apparently due to the instability effect of the director. It is found that shearing substantially affects the structure of the system composed of two mesophase species; specifically, it either facilitates the reinforcement of one of them or provokes structural transitions.     

Self-organizing cyclolinear methylcyclohexasiloxane polymers carrying reactive vinyl groups

Atactic cyclolinear organosilicon polymers containing vinyl substituents in RSiO_1.5, R₂SiO or both moieties have been synthesized through the heterofunctional polycondensation of trans,cis-2,8-dihydroxymethyl(vinyl)cyclohexasiloxanes with 2,8-dichloromethyl(vinyl)cyclohexasiloxanes. The structure of the polymers has been studied by ¹H and ²⁹Si NMR and IR spectroscopy, molecular mass measurements, and elemental analysis. The phase behavior of these copolymers in the bulk has been examined by DSC, X-ray diffraction, and polarization optical microscopy. It has been shown that the copolymer can exist in the mesomorphic state in the temperature range from ?100 to +200°C. The X-ray data indicate changes in the interlayer spacing and the type of packing of cyclolinear poly(methylvinylsiloxanes) with an increase in the content of vinyl substituents in the repeating units of the polymer. The ability of cyclolinear poly(methylvinylsiloxanes) to spread over the water/air interface and to form mono-and multilayers has been investigated. As the content of vinyl substituents in the polymer unit is increased to two or four, the ability of polymers to form multilayers is preserved. The incorporation of vinyl substituents into RSiO_1.5 or R₂SiO moieties of polymer units is accompanied by the formation of monolayers.     

Synthesis and properties of polyetheretherketone–polydimethylsiloxane block copolymers

Polyetheretherketone-polydimethylsiloxane (PEEK–PDMS) block copolymers were synthesized from the condensation of dimethylamino terminated PDMS and hydroxy terminated PEEK oligomers in 1-chloronapthalene. Yields for block copolymers synthesised from low molecular weight PDMS oligomers were good but yields were significantly reduced when higher molecular weight PDMS oligomers were used. This was related to the limited solubility of higher molecular weight PDMS in the reaction solvent. Differential scanning calorimetry (DSC) studies indicated that phase separation of the block copolymers occurred at very short segment length (M?_n < 4000). A depression in the crystallinity of both the PEEK and PDMS phases in the block copolymer was observed. Thermogravimetric analysis (TGA) studies indicated that the PEEK–PDMS block copolymers displayed insufficient thermo-oxidative stability to be melt-processed successfully in PEEK based blends.     

Miscibility behavior and reequilibration of binary poly(amic acid) mixtures

Five poly (amic acid) solutions based on PMDA-PDA, PMDA-ODA, PMDA-6F, ODPA-ODA, and 6FDA-ODA were prepared in N-methylpyrrolidone at a polymer concentration of ca. 10 wt %. From these five poly (amic acid) solutions, six different binary blends were prepared: PMDA-PDA/PMDA-ODA, PMDA-PDA/PMDA-6F, PMDA-ODA/6FDA-ODA, PMDA-ODA/ODPA-ODA, PMDA-PDA/ODPA-ODA, and PMDA-PDA/6FDA-ODA. These blends were then characterized with respect to miscibility in the ternary state (polyamic acid-1/polyamic acid-2/N-methylpyrrolidone), the condensed state (ca. 70 wt % polymer), and the fully imidized state. All blends except for PMDA-PDA/PMDA-6F yielded homogeneous mixtures in the ternary solution of 10 wt % polymer concentration. The PMDA-PDA/PMDA-6F mixture eventually became homogeneous after 10 days of mixing at room temperature. Upon solvent evaporation (condensed state) and full cure (imidized state) two blends incorporating ODPA-ODA as one of the components exhibited apparent miscibility as evidenced by optical microscopy. The remaining blends exhibited large-scale phase separation upon solvent evaporation with no significant differences in the overall morphology between the condensed and imidized state. However, as in the case of the PMDA-PDA/PMDA-6F ternary system, the morphology in the condensed and imidized state was strongly dependent on the mixing time of the precursor poly(amic acid) components; the phase-separated domain size decreased with increasing mixing time, eventually leading to complete miscibility. These results are discussed with respect to the proposed “polymer-monomer” reequilibration reaction as well as its implications with respect to the preparation of polyimide molecular composites.     

ABC copolymer silicone surfactant templating for biomimetic silicification

Using the ABC copolymer silicone surfactant polydimethylsiloxane (PDMS)-graft-(polyethylene oxide (PEO)-block-propylene oxide (PPO)) (PSEP, Scheme 1a) as a template and tetraethoxysilane (TEOS) as a silica source, silica particles with various structures and morphologies (i.e., disordered spherical micellar aggregation, two-dimensional p6mm mesostructure, asymmetric multi-layer non-equilibrium vesicles and symmetric monolayer vesicles) were synthesized by changing the synthesis temperature from 30 to 80 °C. Increasing the hydrophobicity of the surfactant by increasing the temperature resulted in an increase in the surfactant packing parameter g, which led to the mesophase transformation from micellar to cylinder and later to a lamellar structure. The good compatibility between the PDMS and the TEOS, the different natures of the hydrophobic PDMS and PPO segments, and the hydrolysis and condensation rates of TEOS enabled the variation of silicification structures. This novel silicone surfactant templating route and a new type of materials with highly ordered mesostructures and asymmetric morphologies provide a new insight into the molecular factors governing inorganic-organic mesophase and biosilicification for fabricating functionalized materials.     

EFFECT OF MOLECULAR WEIGHT OF PDMS ON MORPHOLOGY AND MECHANICAL PROPERTIES OF PP/PDMS BLENDS

A series of polydimethylsiloxane (PDMS) with varied molecular weights (M_w=3×10~6,1×10~6 and 0.5×10~6) were melt blended with PP to investigate the effect of PDMS molecular weight (MW) on the morphology and mechanical properties of PP/PDMS blends.Scanning electron microscopic (SEM) examination showed that the size of PDMS domains was dependent on the MW of PDMS.It was found that the lower the value of PDMS MW,the better dispersion of the PDMS domains in the PP matrix.Tensile and Izod impact tests reveale...     

（PSF—PDMS—PHS）n／PSF共混物的相容性及表面组成

利用ＤＳＣ、ＤＭＡ、ＴＥＭ和ＸＰＳ对［ＰＳＦ－ＰＤＭＳ－ＰＨＳ］ｎ／ＰＳＦ共混物的相容性及表面组成进行了研究．结果表明，ＰＤＭＳ在共混物表面的富集与ＰＳＦ均聚物和［ＰＳＦ－ＰＤＭＳ－ＰＨＳ］ｎ中硬段的相容性有关；ＰＤＭＳ在相容的共混物体系表面的富集与对应的多嵌段共聚物组成基本相近；不相容共混物体系表面ＰＤＭＳ的富集程度相对较高，当共混物本体中有机硅含量从１％增至５％，表面层ＰＤＭＳ的含量迅速增加，可达到嵌段共聚物中ＰＤＭＳ的含量．     

Phase behavior and anisotropic optical properties of photoluminescent polarizers

The phase behavior and anisotropic optical properties of tensile deformed blends of a photoluminescent polymer guest in an ultra‐high molecular weight polyethylene matrix were studied on the level of single molecules by means of scanning confocal optical microscopy. It is shown that upon tensile deformation of the blends, the system transforms from a phase‐separated system into a quasi‐molecular solid solution. The influence of this phase transition on the anisotropic optical properties of oriented blend films was also investigated with polarized steady‐state photoluminescence spectroscopy. We show that well‐dissolved guest molecules tend to reach higher degrees of orientation at lower draw ratios of the blend films compared to guests that phase‐separate from the matrix polymer. Dichroic ratios in emission in the range of 50 were observed in optimized blend films based on photoluminescent oligomers and linear low density polyethylene.     

Effect of electron beam irradiation on dynamic mechanical,thermal and morphological properties of LLDPE and PDMS rubber blends

The effect of electron beam irradiation on the blends of linear low-density polyethylene (LLDPE) and poly dimethyl siloxane rubber (PDMS) prepared over a wide range of compositions starting from 70:30 to 30:70 (LLDPE: PDMS) by varying the radiation doses from 50 to 300 kGy has been studied. The dynamic modulii and dielectric strength of the blends increase on irradiation at 100 kGy as compared to that for the unirradiated blends. Degree of crystallinity and melting behaviour remain unchanged upon irradiation upto a dose of 100 kGy, beyond which it decreases. Thermal stability increases with increase in the proportion of PDMS rubber in the blend as well as on irradiation at 100 kGy. The phase morphology of the blends examined under the SEM exhibit two phase morphology before electron beam irradiation, whereas single phase morphology is observed after electron beam irradiation due to intra- as well as inter-molecular crosslinking leading to a miscible system.     

Isomorphism within the hexagonal columnar mesophase of molecular and macromolecular self- and co-assembled columns containing tapered groups

The phase behaviour of binary mixtures of self-assembled tapering molecules based on monoesters of oligooxyethylene glycol and 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy]benzoic acid, their corresponding polymethacrylates, and of 4'-methyl (benzo-15-crown-5)-3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy]benzoate within their hexagonal columnar mesophase (Φ_h) is described. The binary blends between molecular tapers co-assemble into a single supramolecular column resulting in isomorphism within their Φ_h mesophase over the entire range of composition. The binary blends between polymethacrylates containing tapered side groups co-assemble into a single Φ_h phase only when the columns of the parent polymers are of similar diameters. This results in binary mixtures which are isomorphic within the Φ_h mesophase over the entire composition range. When the diameters of the columns formed by the parent polymers are dissimilar, isomorphic mixtures are obtained only over a narrow range of composition. Binary mixtures between molecular tapers and macromolecular systems containing tapered side groups co-assemble into a single column to the extent that intercalation of the molecular taper, within the column formed by the macromolecular system containing tapered side groups, is permissible. In all systems increased intracolumnar interactions can be induced by complexation of CF₃SO₃Li by the oligooxyethylenic receptors leading to isomorphism in otherwise non-isomorphic mixtures. Ternary mixtures between molecular tapers with non-specific oligooxyethylenic receptors and specific crown ether receptors and CF₃SO₃ Na as the third component are non-isomorphic within their Φ_h phase due to preferential complexation of the alkali metal cation by the column of the crown ether containing the molecular taper. This results in two columns of dissimilar diameters, which are isomorphic in the Φ_h phase only within a limited range of composition.