Molecular characteristics of polymerized surfactants: influence of introduced crosslinking agent and monomer concentration

Polymerizable surfactants are currently attracting considerable interest due to their promising applications in various fields of science and engineering. The present work is devoted to studies of crosslinked poly(N‐acryloyl‐11‐aminoundecanoic acid) and sodium poly(N‐acryloyl‐11‐aminoundecanoate) that were synthesized in reaction mixtures of various compositions (i.e. with different amounts of a crosslinking agent and monomer concentrations). The products were studied by viscometry, dynamic light scattering, sedimentation velocity ultracentrifugation, flow birefringence as well as equilibrium and non‐equilibrium electric birefringence. It was established that both intramolecular and intermolecular crosslinks are formed in the polymerization process. Molecular optical methods and electro‐optical methods were used to determine the sizes of macromolecules with intramolecular crosslinks and the structures containing intermolecular crosslinks that were prepared at various concentrations of the monomer and the crosslinking agent. It was demonstrated that a simultaneous decrease in the amount of the crosslinking agent and decrease in the initial monomer concentration during the synthesis resulted in a reduction in the number of intramolecular crosslinks and molecular masses of the synthesized crosslinked macromolecules. © 2019 Society of Chemical Industry     

Design and synthesis of zero–zero‐birefringence polymers using N‐methylmaleimide

Zero–zero‐birefringence polymers which exhibit no orientational birefringence and no photoelastic birefringence may be suitable candidates for the components of optical devices. To develop zero–zero‐birefringence polymers, a novel copolymerization system is required. We investigated two types of birefringence of poly(N‐methylmaleimide) (PMeMI) and showed that PMeMI exhibits positive orientational and photoelastic birefringence. On the basis of the results, we calculated the optimal composition for compensating both types of birefringence by solving three equations which describe the relationship between birefringence properties and weight fraction of monomers. When the copolymer compositions were MMA/BzMA/MeMI = 86/8/6 and 88/8/4 (wt %), zero–zero‐birefringence polymers were obtained. By using MeMI as a comonomer, these zero–zero‐birefringence polymers have a much higher glass transition temperature (T_g) than those of previous researches. Also, this polymer film has high transparency comparable with that of PMMA film. Therefore, we conclude that we successfully prepared zero–zero‐birefringence polymers using N‐substituted maleimide and that N‐substituted maleimide is a promising material for zero–zero‐birefringence polymers for optical devices. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40423.     

Macromolecules of poly-(12-acryloylaminododecanoic acid) in organic solvent: Synthesis and molecular characteristics

The samples of poly(12-acryloylaminododecanoic acid) were synthesized in micellar solutions of the monomer. The possibility of obtaining polymeric ionogenic surfactants of different molecular masses by varying concentration of monomeric surfactant was demonstrated. Detailed studies of the obtained polymer were performed using macromolecular hydrodynamic methods, dynamic light scattering, scanning probe microscopy and flow birefringence. The parameter of equilibrium rigidity of macromolecules (the Kuhn segment length A = 62 × 10⁻⁸ cm) and their effective hydrodynamic diameter were determined in mixed solvent (dioxane-cyclohexanol). Contributions made by optical microform and macroform effects to the observed dynamic birefringence were analyzed in detail. The intrinsic optical anisotropy of the monomer unit was estimated; it correlates well with the corresponding values for comb-shaped polymers of similar structure.     

Synthesis and evaluation of properties of poly(p‐phenylenevinylene) based 1,3,4‐oxadiazole systems for optoelectronics and nonlinear optical applications

Two new π‐conjugated polymers, namely poly(p‐phenylenevinylene‐1,3,4‐oxadiazole) (PPVO) and poly(p‐(nitro‐phenylene)vinylene‐1,3,4‐oxadiazole) (PNPVO), were synthesized and characterized. The Gilch polymerization technique, using dihalo derivatives of 1,3,4‐oxadiazoles, was employed to synthesize them under mild reaction conditions. The macromolecules exhibit good solubility in dimethylformamide, formamide and dimethyl sulfoxide and thus effectively address the insolubility issues associated with many oxadiazole derivatives for device fabrication. They show bright luminescence in the blue‐green region of the electromagnetic spectrum and have optical band gaps suited for an emissive layer in organic light‐emitting devices. PPVO and PNPPO show good non‐linear optical responses also in solution phase, with third‐order nonlinear susceptibilities of the order of 10^?12esu. Interestingly, they exhibit good antimicrobial characteristics under examination with Escherichia coli and Staphylococcus. The results prove that these macromolecules are ideal materials to use as emissive layers in various light‐emitting devices and NLO applications. The excellent antimicrobial activity can be utilized for their applications in clinical and healthcare areas. © 2016 Society of Chemical Industry     

Synthesis and properties of novel crosslinkable second‐order nonlinear optical polymers based on 2,3,4,5,6‐pentafluorostyrene

Two crosslinkable second‐order nonlinear optical polymers were prepared by copolymerization of 2,3,4,5,6‐pentafluorostyrene, styrene (St), glycidyl methacrylate (GMA) and 1‐(4‐nitrophenyl)‐2‐(4‐{[2‐(methacryloyloxy) ethyl] ethylamino}‐phenyl) diazene (DR1M) via the sealed‐tube reaction technique. These polymers were characterized using ¹H, ¹³C and ¹⁹F NMR spectroscopy, gel permeation chromatography (GPC), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The crosslinkable polymers have high molecular weights, good organosolubility, excellent film‐forming properties and high glass transition (106–110 °C) and thermal decomposition temperatures (290–350 °C) after being crosslinked. Furthermore, the polymer films possess not only high values (12–16 pm V^?1) of electro‐optical coefficient (r₃₃) at 1.3 µm wavelength but also low optical loss (1.7 dB cm^?1) at 1.55 µm wavelength, which is of interest for applications in electro‐optical devices. Copyright © 2004 Society of Chemical Industry     

Influence of process parameters on the structure formation of man‐made cellulosic fibers from ionic liquid solution

The influence of dry‐jet wet spinning parameters on the production of man‐made cellulosic fibers from 13 wt % cellulose/1,5‐diazabicyclo[4.3.0]non‐5‐ene acetate solutions was investigated. The spinneret nozzle diameter, extrusion velocity, draw ratio, and coagulation bath temperature were the studied parameters. The production of highly oriented fibers was favored by selecting higher extrusion velocity and lower spinneret diameter. A spinneret size of 100 µm and a draw ratio of 6 were sufficient to highly orient the cellulose macromolecules and achieve tenacities above 40 cN/tex (600 MPa). Total orientation assessed via birefringence measurement, tenacity, and Young's modulus values reached a plateau at a draw of 6 and no further development in properties was observed. A temperature of the aqueous coagulation bath of 15 °C slightly promoted greater orientation of the fibers by hampering structural changes of the cellulose macromolecules in the nascent solid fibers. Furthermore, the determination of the elongational viscosity of the liquid thread via the measurement of radial force tensor was tested and showed promising results. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43718.     

Electro-optical Properties, Polarity and Chain Rigidity of Poly(dialkoxyphosphazene)s with Variable Side-Chain Length

Molecular properties of poly(dialkoxyphosphazene) (PDAOP) series with the aliphatic side-chains contained 3, 4, 6, and 7 carbon atoms were investigated in dilute benzene solutions by techniques of electro-optical Kerr effect and dynamo-optical Maxwell effect, and by dielectric spectroscopy. The sign inversion of Kerr effect and Maxwell effect in PDAOP solutions from positive to negative was detected at the side-chain length range of 5–6 carbon atoms. These phenomena were explained by the strong dependence of anisotropy of optical polarizability of PDAOP monomeric unit on chemical structure and change of its sign at the indicated side-chain lengths. It was demonstrated that PDAOPs possess a critical side-chain-length interval at which their physical properties, depending on the intramolecular ordering, display a singularity. It was also shown that the studied PDAOP samples are not flexible-chain polymers. They are characterized by Kuhn segment 47–65 Å, the value of which increases with the elongation of aliphatic side-chain. Dielectric properties of PDAOP were correlated to the properties of the macromolecules with manifestation of kinetic rigidity under a treatment of electric field.     

Recent advances on polymer‐stabilized blue phase liquid crystal materials and devices

Polymer‐stabilized blue phase liquid crystals (PS‐BPLC) have become an increasingly important technology trend for information display and photonics applications. BPLCs exhibit several attractive features, such as reasonably wide temperature range, submillisecond gray‐to‐gray response time, no need for alignment layer, optically isotropic voltage‐off state, and large cell gap tolerance. However, some bottlenecks such as high operation voltage, hysteresis, residual birefringence, charging issues due to the large capacitance, and relatively low transmittance remain to be overcome before their widespread applications can be realized. Recent progress on BPLC materials and devices has shown great promise. To realize the electro‐optic effect of PS‐BPLC, two driving modes: in‐plane switching and vertical field switching mode, have been developed. The material system of PS‐BPLC, including nematic LC host, chiral dopant, and polymer network, are discussed. Each component plays an essential role affecting the stability and electro‐optic properties of PS‐BPLC. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40556.     

Post and prepolymerization strategies to develop novel photochromic poly(esterimide)s

This paper reports novel photoresponsive, processable poly(esterimide)s functionalized with the azobenzene and tricyanovinylene groups. Post and prepolymerization strategies were utilized for preparation of the new photochromic polymers with imide rings. The postpolymerization method of azopolymer synthesis included a functionalization of precursor poly(esterimide) containing dialkylaminophenyl groups with diazonium salt of aniline. The precursor poly(esterimide) was obtained from synthesized 2,2′[N‐phenylethyloaniline‐di(4‐estro‐1,2‐dicarboxylic)]anhydride and 4,4′‐methylene bis(2,6‐dimethylaniline). The prepolymerization strategy based on polycondesation of 2,4‐diaminoazobenzene with two dianhydrides, that is, with or without the azobenzene group. The new dianhydride with azobenzene unit was obtained. The reaction of post‐tricyanovinylation was carried out for substitution of prepared polymers with tricyanovinylene groups. The synthesized polymers were characterized and evaluated by FTIR, ¹H NMR, X‐ray, UV‐Vis spectroscopies, and DSC. The polymers exhibited glass transition temperatures in the range of 119–208°C and good solubilities in common organic solvents, providing optical‐quality films. Thermal stability of the polymers films was investigated by UV‐Vis spectroscopy. Preliminary investigations of the optical anisotropy in chosen poly(esterimide)s were carried out by photoinduced birefringence measurements. Relatively high photoinduced birefringence (Δn = 0.01) was measured for polyimide with covalently bonded azobenzene substituted with strong acceptor group. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Optical anisotropy of polyisobutene

The distribution of chemical bonds in polyisobutene results in a theoretically zero optical and electrical anisotropy of the polymer according to bond polarizability additivity principles as conventionally applied, irrespective of polymer chain conformation. Non-zero values of the segmental anisotropy (～4.4 × 10^?40 C²m²/J) derived from strain-optical birefringence on the polymer in the rubbery state have been recently reported by Liberman et al. who suggest qualitatively that severe crowding of the chemical groups in the polymer affects the anisotropies of the group polarizabilities and gives the observed non-zero segmental anisotropy. We have measured optical, electrical and magnetic anisotropies for the pure liquid polymer using techniques of flow birefringence, depolarized light scattering, electro-optic birefringence and magneto-optic birefringence. Segmental optical anisotropies so derived agree with those measured by Liberman et al. and results of the above measurements taken as a whole lead to an origin for the observed anisotropy which requires locality dependent values of optical and electrical bond polarizability anisotropies to be used in the calculation of the polyisobutene polarizability anisotropy. Our explanation of the polarizability locality dependence differs from the steric overlap suggestion of Liberman et al. and depends upon the electric field interaction between dipoles induced in polarizable bonds.     

Opto‐thermal properties of fibers. XV. A study of the drawing behavior of quenched poly(ethyleneterephthalates) fibers

Studies of the mechanical and optical properties of undrawn uniaxially stretched polyester PET (Egyptian manufacture) fibers by annealing and cold drawing were performed. The optical properties and strain produced in PET fibers at different conditions were measured interferometrically at room temperature. A two‐beam interferometric technique was used to determine refractive indices and birefringence of the investigated PET samples with strain produced by different stresses. Using a microstrain device attached to a microscope stage and through the application of the appropriate mathematical equations, the refractive indices and the birefringence values were determined as a function of the draw ratios. The resulting data were utilized to calculate the polarizability per unit volume, the number of molecules per unit volume, Poisson's ratio, the strain optical coefficient, and several other parameters and constants. Also, some structural parameters are determined, such as form birefringence, the virtual refractive index, the harmonic mean polarizability of the dielectric, the harmonic mean specific refractivity, and the isotropic refractive index. The generalized Lorentz–Lorenz equation given by de Vries is used to determine PET fiber structure parameters. Comparison between the results have been compared with Hermans' optical orientation function. Relationships between the various optical parameters and the draw ratios are plotted, and the effect of draw ratio on the refractive index profile is studied. Microinterferograms are given for illustration. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1869–1880, 1999     

Fluorene‐based click polymers: Relationship between molecular structure and nonlinear optical properties

To further understand the relationship between the polymer structure and nonlinear optical (NLO) property, in this article, three fluorene‐based triazole functional polymers with different linked chains were designed and controllably prepared by click chemistry method. The structures and properties of these polymers were characterized and evaluated with Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, ultraviolet spectroscopy, fluorescence spectra, dynamic state laser light scattering, thermogravimetric analysis, and NLO analyses. The results exhibited that the target polymers displayed good solubility, high thermal stability, and well NLO properties. The relationships between molecular structures and optical properties were investigated by both theoretical simulation and experimental results. It was found that the rigid conjugated linked chain between triazole and chromophore can effectively enhance the NLO properties of the resultant polymers. The suitable rigid and flexible groups in the triazole polymers will result in good thermal stabilities. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40878.     

Optical nonlinearity and photoinduced anisotropy of an azobenzene‐containing ionic liquid crystalline polymer

The nonlinear optical properties of an azobenzene‐containing ionic liquid crystalline polymer were investigated using single‐beam Z‐scan and optical Kerr effect (OKE). The polymer film exhibited large nonlinear absorption (～10^?6 cm W^?1) and nonlinear refraction (～10^?11 cm² W^?1) under 532 nm ps excitation. The femtosecond time‐resolved OKE results suggested that the nonlinear optical response time in off‐resonant region was as fast as 300 fs. Moreover, stable molecular reorientation and a large photoinduced birefringence ( ) were achieved in the polymer film with a 405 nm continous wave (CW) laser as pump light. The large optical nonlinearity, ultrafast response, and effective photoinduced molecular reorientation of the polymer films indicated their potential applications in nonlinear photonic devices and optical storage. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Macro reversible addition–fragmentation chain transfer agent mixture as a means to enhance the electro‐optical performance of polymer‐dispersed liquid crystals

Macro reversible addition–fragmentation chain transfer (RAFT) agents, i.e. RAFT polystyrene (RAFT‐PS) and RAFT poly(n‐butyl acrylate) (RAFT‐PBA), were mixed. Polymer‐dispersed liquid crystals (PDLCs) were prepared using the mixture together with methyl acrylate and liquid crystal E7. The electro‐optical properties of the PDLCs obtained were investigated. The results showed that the advantages of the electro‐optical properties of RAFT‐PS‐ and RAFT‐PBA‐dependent PDLCs could be combined in RAFT agent mixture‐dependent PDLCs. Copyright © 2011 Society of Chemical Industry     

Optoelectronic properties of thiazole‐based polythiophenes

In this work, two thiazole‐containing monomers N‐(thiazol‐2‐yl)?2‐(thiophen‐3‐yl)acetamide (ThDBTH) and N,N′‐([4,4′‐bithiazole]‐2,2′‐diyl)bis(2‐(thiophen‐3‐yl)acetamide) (Th₂DBTH) were synthesized through amidification reaction of 2‐(thiophen‐3‐yl)acetyl chloride with aminothiazole derivatives and characterized by FTIR and ¹H and ¹³C‐NMR. The monomers were subjected to electrochemical polymerization and optoelectronic properties of the resultant conducting polymers were investigated. Additionally, copolymerization of ThDBTH in the presence of thiophene was achieved. PThDBTH, PTh₂DBTH, and P(ThDBTH‐Th) exhibited optical band gaps of 2.15, 2.30, and 1.95 eV, respectively. Switching time and optical contrast of the polymers were evaluated via kinetic studies. The P(ThDBTH‐Th) revealed satisfactory switching time and appropriate optical contrast of 1.27 s and 24.97%, respectively. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42206.     

Europium‐containing cholesteric liquid crystalline polymers in the side chain

Europium‐containing cholesteric liquid crystalline polymers were graft copolymerized using poly(methylhydrogeno)siloxane, cholesteryl 4‐(allyloxy)benzoate (M₁), cholesteryl acrylate (M₂), and a europium complexes monomer (M₃). The chemical structures of the monomers were characterized by Fourier transform infrared and ¹H‐nuclear magnetic resonance. The mesomorphic properties and phase behavior were investigated by differential scanning calorimetry, thermo gravimetric analysis, polarizing optical microscopy, and X‐ray diffraction. With an increase of europium complexes units in the polymers, the glass transition temperature (T_g) did not change significantly; the isotropic temperature (T_i) and mesophase temperature range (ΔT) decreased. All polymers showed typical cholesteric Grandjean textures, which was confirmed by X‐ray diffraction. The temperatures at which 5% weight loss occurred (T_d) were greater than 300°C for the polymers. The introduction of europium complexes units did not change the liquid crystalline state of polymer systems; on the contrary, the polymers were enabled with the significant luminescent properties. With Eu³⁺ ion contents ranging between 0 and 1.5 mol %, luminescent intensity of polymers gradually increased and luminescent lifetimes were longer than 0.45 ms for the polymers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40866.     

Surface roughness effect on optical loss in waveguide using isotropically induced crosslink network of siloxane–polyimide copolymer

Optical properties of two-fluorinated polysiloxane-co-polyimide (PI-PDMS and 3-(aminopropyl)triethoxysilane [PI-APTES]) were investigated based on their molecular structure and compared with the pure PI at 1,550 nm radiation. The refractive indexes and birefringence of the copolymers were reduced which is attributable to the chain flexibility as substantiated from the differential scanning calorimetry result. They are highly transparent at near infrared (NIR) region with light transmittance above 90% at visible region while displaying excellent thermal stability up to 456°C. Asymmetry planar waveguides was fabricated which recorded a respectable low optical loss 0.020 dB/cm for pure PI, 0.042 dB/cm for PI-PDMS, and 0.066 dB/cm for PI-APTES, respectively. Despite proving low NIR absorption and low birefringence, extrinsic factor namely surface roughness was accounted as affecting the higher optical loss in polyimide siloxane copolymer compared to pure PI. The excellent thermal and optical properties displayed by these series of material established their viable application as waveguide material at 1,550 nm wavelength.     

Optical anisotropy and non-linear optical properties of azobenzene methacrylic polymers

Photoinduced optical anisotropy has been studied in several methacrylic copolymers, either amorphous or liquid crystalline, with cyano azobenzene chromophores in the side chain. Illumination with linearly polarised 488 nm light gives rise to high and stable values of birefringence and dichroism, mainly in liquid crystalline films. Both dichroism and birefringence decrease with the azo content in the copolymer series while some increase can be achieved by the incorporation of biphenyl molecules to the copolymers. Photoinduced anisotropy disappears above the glass transition temperature in amorphous polymers, whereas it increases in liquid crystalline polymers (LCP) due to a thermotropic self-organisation.The non-linear optical (NLO) properties of the films have been studied by second harmonic generation (SHG) measurements. The intensity of the harmonic signal from in situ corona poled polymeric films has been measured. The effect of 488 nm light irradiation on the azo chromophores orientation and consequently on the NLO response of the films was investigated at different temperatures. The intensity and thermal stability of the second harmonic signals obtained after the two different (thermal and photoassisted) corona poling processes have been compared.     

Effect of the molecular architecture of side radicals on the optical properties of comb-shaped polymers

The optical properties of four comb-shaped polymers of the methacrylic series with different optically anisotropic groups in side chains are studied by the methods of flow birefringence and viscometry. The experimental values of the optical anisotropy are compared with theoretical estimates calculated in terms of the additivity principle of polarizabilities of valence bonds. It is shown the optical properties of comb-shaped polymers significantly depend on the position (even or odd) of optically anisotropic side groups relative to the main chain.     

Effect of fluorinated substituents on hydrodynamic and conformational properties of hyperbranched polycarbosilane in solutions

Fractions of hyperbranched polycarbosilane modified with fluorine-containing end groups are studied by the methods of molecular hydrodynamics and optics in dilute solutions in hexafluorobenzene, methyl tert-butyl ether, chloroform, tetrahydrofurane, and toluene. The results are compared with the data available for the original polymethylallylcarbosilane. The incorporation of fluorinated groups leads to a change in the hydrodynamic parameters of the hyperbranched polymer. In this case, in thermodynamically better solvents, the patterns of the molecular-mass dependence of intrinsic viscosity for fluorinated and original hyperbranched polycarbosilanes coincide since the macromolecules of the polymers under comparison are characterized by similar shapes and almost the same hydrodynamic sizes. In a thermodynamically worse solvent (toluene), the above-mentioned changes in hydrodynamic parameters and the character of the molecular-mass dependences are related to compaction of macromolecules and a decrease in their shape asymmetry. This tendency is probably associated with the selectivity of this solvent with respect to the fluorine atom.