Consequences of Chemical Modification on Optical and Solution Properties of Rodlike Polyamides

Abstract

Rodlike polyamides were substituted to 50–55% on the nitrogen atom of the amide group with benzyl, 1-naphthylmethyl, and 4-(1,3,6,8-tetrabromo-9-carbazolyl)-1-butyl groups using a standard literature procedure. The resulting polymers exhibit significantly lower isotropic refractive indices and enhanced solubility. Polymers composed of the isophthaloyl moiety, with or without N-substitution, also exhibit lower refractive indices and enhanced solubility when compared to their rodlike analogs. These differences in properties are due to a great extent to the large difference in conformational rigidity between the two polymer types.     

Polyamides containing thiadiazole units: Synthesis and optical properties

Highly refractive and transparent polyamides containing thiadiazole units have been developed.These polymers were prepared by a polycondensation reaction of 4,4'-(1,3,4-thiadiazole-2,5-thio) bis(methylene) dibenzoyl chloride(TDTBM-DC) and diamine which contained thioether(―S―) and sulfone units.They showed good thermal stabilities such as a relatively high glass transition temperature of 206-233 °C and a 5% weight-loss temperature(T5%) of 376-395 °C.The optical transmittance of the polymer at 450 nm is higher than 83%.The heterocycle units and plural ―S― linkages provide the polymer with a high refractive index of 1.716-1.725 at 633 nm and a low birefringence of 0.003-0.004.Also they showed improved solubility in polar aprotic solvents and could form moderate strength films with tensile strength of 72.8-83.1 MPa and storage modulus of 1.0-1.8 GPa(at 200 °C).     

Form birefringence in biaxially oriented polypropylene

The birefringence of several biaxially oriented polypropylene films swollen with a number of fluids has been measured and found to exhibit a minimum when plotted against the fluid refractive index, as predicted by the theory of Wiener. However, a discrepancy in the form birefringence behavior is observed when samples of different degrees of crystallinity but the same total birefringence are compared. These results are interpreted in terms of Bullough's theory and suggest that this discrepancy arises because of different morphologies. A refractometric technique was employed that makes possible the simultaneous determination of birefringence and the volume fraction of fluid.     

Synthesis and evaluation of properties of novel poly(benzimidazole‐amide)s

Novel aromatic polyamides have been prepared by a combination of diacids containing preformed benzimidazole rings and aromatic diamines. By the phosphorylation method of polycondensation, polymers of high molecular weight (inherent viscosities between 0.81 and 2.13 dL/g) were obtained, which showed good solubility in polar aprotic solvents. The combination of aromatic amide linkages and benzimidazole rings along the polymer chain endowed the polymers with high thermal resistance and excellent mechanical properties. Glass transition temperatures fell in the range of 290–330 °C as measured by differential scanning calorimetry, and initial decomposition temperatures under nitrogen were over 480 °C as measured by thermogravimetric analysis. Some polymer films showed outstanding tensile strength (over 150 MPa) and moduli (up to 5 GPa). The presence of benzimidazole rings in the current polyamides greatly enhanced their hydrophilicity in comparison with classical wholly aromatic polyamides; thus, although aromatic polyamide films normally show water sorption values of only 4–8%, some of the current poly(benzimidazole amide)s show water sorption up to 19% in a 65% relative humidity atmosphere. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7566–7577, 2008     

Molecular Composites Comprising Rodlike Polyamides and Vinyl Polymers

Abstract

At present we have strong evidence that several members of a series of wholly-aromatic, para-linked, rodlike polyamides, polyesters, and polyesteramides form molecular composites with certain flexible-chain, thermoplastic polymers over a wide range of compositions. This paper reports on the initial results of an investigation of intermolecular interactions using spectroscopy and various scattering techniques as well as characterization of some of the mechanical and optical properties of these materials. The composites are made by two techniques: 1) photo-polymerization of a homogeneous solution of a rodlike polymer in a monomer containing a photoinitiation; 2) solvent evaporation from homogeneous solutions of very limited combinations of solvent, rodlike polymers and flexible polymers. While both of these techniques produce optically clear, nonscattering films of various thicknesses over the entire compositional range, e.g., 1–99 wt% of rodlike polymer, the latter is generally more convenient and has been used extensively in this study. Optical and electron microscopy, wide angle light scattering, and spectroscopic and thermal analysis support the view that these polymer combinations are truly molecularly dispersed.     

An All‐Inorganic Colloidal Nanocrystal Flexible Polarizer

Inorganic single crystals with anisotropic structures usually suffer from high brittleness and stiffness. Flexible polymers are used to replace inorganic crystals, but the hot‐stretching‐induced orientation process is tedious, and oriented molecular chains tend to revert to random coils during aging. To overcome these obstacles and using the similarities between sub‐1 nm nanowires (NWs) and linear polymers, we successfully fabricated anisotropic, transparent, flexible, and stable (ATFS) NW films with great potential for optical applications through a wet‐spinning method. The NW films show birefringence, and their birefractive index is higher than that of many polymers. They also showed polarized absorption of UV light and anisotropic scattering of visible light. The integrated films composed of NWs and quantum dots showed good fluorescence polarization. The tedious synthesis of quantum rods and fabrication of oriented polymer films can thus be avoided.     

High-refractive index acrylate polymers for applications in nanoimprint lithography

The development of polymeric optical materials with a higher refractive index,transparency in the visible spectrum region and easier processability is increasingly desirable for advanced optical applications such as microlenses,image sensors,and organic light-emitting diodes.Most acrylates have a low refractive index(around 1.50)which does not meet the high perfo rmance requirements of advanced optical materials.In this research,three novel acrylates were synthesized via a facile one-step approach and used to fabricate optical transparent polymers.All of the polymers reveal good optical properties including high transparency(≥90%)in the visible spectrum region and high refractive index values(1.6363)at 550 nm.Moreover,nanostructures of these acrylate polymers with various feature sizes including nanogratings and photonic crystals were successfully fabricated using nanoimprint lithography.These results indicate that these acrylates can be used in a wide range of optical and optoelectronic devices where nanopatterned films with high refractive index and transparency are required.     

Effect of dopant structure on refractive index and glass transition temperature of polymeric fiber‐optic materials

Graded‐index plastic optical fibers, composed of doped polymers, have advantages over conventional glass optical fibers, but need to be developed further for practical application. Here, a variety of aromatic sulfide dopants were synthesized, and their effects on the refractive indexes and glass transition temperatures (T_g) of poly(methyl methacrylate) and methyl 2‐chloroacrylate/2,2,2‐trichloroethyl methacrylate copolymers were studied. While polymers containing large dopants exhibited relatively high refractive indices, their T_g values were low, making these materials unsuitable for graded‐index plastic optical fiber applications. Six dopants yielded polymers that exhibited higher T_g values than the conventionally used (diphenyl sulfide)‐doped polymer. The dopant dibenzothiophene, in particular, yielded polymers with the highest refractive indexes and T_g values, and polymers containing (phenylthio)benzene dopants also performed well. Copyright © 2013 John Wiley & Sons, Ltd.     

Phenothiaphosphine-containing polyamides and polyesters

Phosphorus-containing polyamides and polyesters, which had tricyclic fused rings (phenothia-phosphine rings) in the main chain, were prepared and the properties of the resulting polymers were examined. These polymers were obtained at highly reduced viscosities in satisfactory yields by the polycondensation of 2,8-dichloroformyl-10-phenylphenothiaphosphine 5,5,10-trioxide with aromatic diamines or bisphenols. The polyamides and polyesters were soluble in polar aprotic solvents such as dimethylacetamide and N-methyl-2-pyrrolidone; the polyesters were also soluble in chloroform. The polymers exhibited good heat resistance. The phenothiaphosphine-containing polyamides and polyesters self-extinguished immediately when flame was removed and were highly flame-resistant. The polyester obtained from bisphenol A showed a limiting oxygen index value of 43.5.     

Studies of orientation and structure of crazed matter in polystyrene. I. Optical measurements

The optical birefringence and refractive index have been measured for crazes grown in specimens of varying thickness. The birefringence was found to consist of the sum of a small negative orientation term and a large positive form term. The latter term could be altered by filling the craze with liquids of various different refractive indexes. Two crazes, which showed a relatively constant width as the specimen thickness changed, could be described by a model with craze having a constant refractive index and birefringence but with impervious dense skins on either side. The numerical value of the form birefringence was approximately 0.6 of that predicted from a model of parallel rods which is not surprising as crazes have a networklike structure. The values of craze refractive index were in good agreement with other measurements. The existence of skins, of thickness approximately 300 nm, places some doubt on the relevance of thin-film electron microscope observations to the situation in the bulk. Other crazes which tapered in width were found to show both varying skin thickness and refractive index along their length.     

Effect of trifluoromethyl substituents on birefringence of polystyrene

Transparent thermoplastic polymers that exhibit no birefringence are ideal for optical components such as optical films for liquid crystal displays and various lenses. Copolymerization of a positive birefringent monomer with a negative monomer is an effective technique for obtaining low birefringent polymers, especially zero‐photoelastic birefringence polymers that exhibit no photoelastic birefringence even during elastic deformation. We prepared four types of trifluoromethyl‐substituted polystyrenes. By substituting hydrogens at the ortho or meta positions of the benzene ring of polystyrene, we demonstrated that poly(2‐(trifluoromethyl)styrene), poly(3‐(trifluoromethyl)styrene), and poly(3,5‐bis(trifluoromethyl)styrene) had negative photoelastic coefficients. However, poly(4‐(trifluoromethyl)styrene) had a positive photoelastic coefficient similar to that of polystyrene. Based on these results, we synthesized a zero‐photoelastic birefringence polymer of poly(2‐(trifluoromethyl)styrene‐co‐4‐(trifluoromethyl)styrene) (55/45 wt.) exhibiting no photoelastic birefringence in elastic deformation, in which the positive photoelastic birefringence of the poly(4‐(trifluoromethyl)styrene) unit was compensated for by the negative photoelastic birefringence of the poly(2‐(trifluoromethyl)styrene) unit. The discovery of polymers having negative photoelastic coefficients is valuable for the design and synthesis of zero‐photoelastic birefringence polymers. The four types of trifluoromethyl‐substituted polystyrenes are promising optical materials because they have high transparency (transmittance > 89–92% for 27–34‐µm thickness films) in the visible and near‐infrared regions and a high decomposition temperature of approximately 400°C. Copyright © 2016 John Wiley & Sons, Ltd.     

Infrared spectral study of noncrystalline rodlike polymers

Oriented and unoriented films of noncrystalline, wholly-aromatic, rodlike polyamides, and polyesteramides were examined by infrared spectroscopy. The results indicate that orientation, accomplished by means of mechanical stretching, approaches 80% in both polymer classes. Examination of the NH and the CO stretching region revealed an increase in the population of nonhydrogen bonded species (plateauing at ～ 85%) as orientation increases. This unusual result may be caused by interchain steric interactions which may also be responsible for both the noncrystalline morphology and the non-lyotropic behavior exhibited by these polymers.     

Orientation analysis of uniaxially drawn polycarbonate films,doped with fluorescent molecules,by UV-dichroism,fluorescence polarization and birefringence

Bis-phenol-A-polycarbonate (PC) is dyed in solution with fluorescent molecules of different shapes and cast to films. Rectangular samples, cut from these films, are drawn varying draw ratio and drawing temperature. The orientation of the fluorescent probes is investigated by dichroism and fluorescence polarization, that of the polymer segments by birefringence. Hermans' orientation factors obtained by dichroism and fluorescence polarization are in good agreement. Long rodlike fluorescent molecules exhibit greater orientation factors than smaller ones. The correlation between segmental and probe orientation is discussed. Keeping the birefringence constant, the probe orientation factors depend on drawing temperature.     

Aromatic polymers with side oxadiazole rings as luminescent materials in LEDs

Aromatic polyamides and polyazomethines with side oxadiazole rings have been synthesized by using aromatic diamines containing pendent substituted oxadiazole groups and a diacid chloride having diphenylsilane or hexafluoroisopropylidene, or an aromatic dialdehyde with fluorene unit, respectively. These polymers were easily soluble in amidic solvents. Very thin films which were deposited from polymer solutions onto silicon wafers exhibited smooth, pinhole-free surface in atomic force microscopy investigations. The polymers showed high thermal stability with decomposition temperature being above 400°C. Some of them exhibited blue photoluminescence, in the range of 450-480 nm, making them promising candidates for future use as high performance materials in the construction of light emitting devices.     

Optical anisotropy in solution-cast film of cellulose triacetate

The out-of-plane birefringence and its wavelength dispersion are studied employing solution-cast films of cellulose triacetate (CTA). In solution-cast process, CTA molecules are induced to align in the film plane. Although refractive index is the lowest in the oriented direction for the CTA films stretched more than 110 %, refractive index is found to be the lowest in the normal direction for the unstretched cast film. Attenuated total reflection measurements reveal that in-plane alignment of the acetyl group which provides strong polarizability anisotropy is responsible for the phenomenon. Furthermore, the out-of-plane birefringence is found to increase with increasing wavelength, i.e. extraordinary wavelength dispersion, whereas a stretched CTA film shows ordinary wavelength dispersion. The level of the out-of-plane birefringence in cast films depends on the preparation conditions, which is predictable considering the evaporation rate. Moreover, it is demonstrated for the first time that the out-of-plane birefringence and its wavelength dispersion can be modified by addition of a certain plasticizer such as tricresyl phosphate (TCP). During the evaporation, TCP molecules orient in the film plane accompanying the orientation of CTA chains by intermolecular orientation correlation, called nematic interaction. This technique will widen the scope of material design of retardation films because there are numerous liquid compounds having strong polarizability anisotropy.     

Quasi-isotropic analysis of anisotropic thin films on optical waveguides

Thin films assembled on a substrate are often anisotropic. Nevertheless, because of experimental limitations, sufficient parameters to characterize the anisotropy, even in the simplest (and perhaps most common) case of uniaxial thin films, which are birefringent, are not usually available. This paper examines the consequences of treating them as isotropic thin films, with particular reference to their characterization via perturbation of the propagation constants (effective refractive indices) of optical waveguides. It is shown that the refractive index and geometrical thickness of a thin film thus calculated are often unrealistic (especially when the thin film is positively birefringent), but the mass per unit area may be quite precise, depending on the sign and magnitude of the birefringence.     

Synthesis of silyl-functionalized oligothiophene-based polymers with bright blue light-emission and high refractive index

In this paper, we report the synthesis of partially conjugated polymers with a silyl-group-substituted oligothiophene and a short alkyl chain in the main chain by hydrosilylation polymerization and describe their optical properties such as luminescence and refractive index. The obtained polymers are found to have good solubility and processability. Moreover, the high steric hindrance of the silyl-group can inhibit the π-π interaction and intermolecular aggregation of the polymers. Hence, the emission of the obtained polymers was similar to that of the corresponding silyl-group-substituted oligothiophene. The polymers exhibit intense light blue fluorescence under UV irradiation and a high refractive index in the visible light region.     

Stress in polyimide coatings

The effect of film thickness on in-plane molecular orientation and stress in polyimide films prepared from pyromellitic dianhydride with 4,4′-oxydianline was investigated using a prism coupling technique to measure the refractive index. Film thickness was controlled by varying both solution concentration and spinning conditions. Birefringence, the difference between the in-plane and out-of-plane refractive indices, was used to characterize the in-plane molecular orientation. The observed birefringence is a combination of the birefringence resulting from molecular orientation and the birefringence induced by the residual stress present in the films. The birefringence decreases with increasing film thickness over the range of thicknesses studied (3–20 μm) indicating that the molecular orientation decreases with increasing film thickness. The in-plane coefficient of linear thermal expansion (CTE), controlled by the level of orientation in the film, increases from 18 to 32 × 10^?6/°C over the same thickness range. The birefringence of free-standing films was lower than that of adhered films due to the release of residual stress in the film once the film is removed from the substrate. The residual film stress arises primarily from the mismatch in CTEs between the polyimide film and the substrate to which the film is adhered. Thus, since the film anisotropy decreases with increasing thickness, the film stress increases with increasing thickness. Residual stress calculated by integrating the product of the film modulus and the CTE mismatch assuming temperature-dependent properties is comparable to experimentally measured film stress. Ignoring the temperature dependence of the film properties leads to an overestimation of stress. Moisture uptake was used to study the stress dependence of the optical properties. Moisture uptake increases both the in-plane and out-of-plane refractive indices by equal amounts in free-standing films due to an isotropic increase in the polarizability. In adhered films, an increase in moisture uptake leads to a decrease in the birefringence due to a swelling-induced decrease in the residual film stress. © 1994 John Wiley & Sons, Inc.     

Polyamides with pendant 1,3,4-oxadiazole and pyridine moieties

A novel aromatic diamine,2-（5-（3,5-diaminophenyl）-l,3,4-oxadiazole-2-yl）pyridine（POBD）,containing a pyridine ring and a 1,3,4-oxadiazole moiety,was synthesized.It was used in a polycondensation with various aromatic and aliphatic diacid chlorides to generate a series of new aromatic polyamides with pendant 1,3,4-oxadiazole groups.The prepared polyamides were characterized by IR,elemental analysis and through the synthesis of model compounds.Thermophysical properties of the synthesized polyamides have been studied by DSC,TGA and inherent viscosity measurements. Relatively high inherent viscosity values（0.76-1.62 dL/g,in 0.125%H₂SO₄ at 25℃） were observed for these compounds. Number average molecular weight（M_n） of the polymers was measured by vapor phase osmometry（VPO）.The introduction of bulky side chains in the structure of aromatic polyamides led to increased solubility of these polymers in common polar and aprotic solvents,such as DMF,DMSO,NMP and DMAc,which allowed thin films to be cast from polymer solutions. The highest molecular weight（M_n = 51190） was observed for polymer（DC）,which was prepared from pyridine-2,6-dichlorocarbonyl.     

A novel generation of photoactive comb‐shaped polyamides for the photoalignment of liquid crystals

A new approach to the synthesis of photoactive comb‐shaped homo‐ and copolyamides containing azobenzene, cinnamate, and coumarin side groups for photoalignment of liquid crystals was elaborated. Photooptical properties and photoorientational ability of these polymers with respect to liquid crystals were studied. It was shown that polarized UV irradiation of all spin‐coated polyamides leads to orientation of liquid crystalline molecules deposited on the polyamide thin films. The synthesized polymers containing cinnamate and coumarin side groups as well as azobenzene‐containing cyano‐ and nitro‐substituted polymers demonstrated good orientation ability in relation to liquid crystals displaying photoinduced planar orientation with high dichroism values within the range of 0.68–0.72. Contrary to the above‐mentioned polyamides, azobenzene‐containing fluorosubstituted polymers induced a homeotropic orientation of liquid crystals. It was shown that the synthesized photoactive polyamides can be considered as promising photoalignment materials for application in display technology, photonics, and other “smart” optical devices. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4031–4041