Electro-optical properties and nonlinear response of side chain liquid crystalline polymers

Among the NLO processes that have been studied, one of the most visually dramatic is the frequency doubling. In the field of optical information storage this process can provide the conversion of near-infrared laser light from diode lasers into deep blue light. Compared to the more traditional inorganic NLO materials, polymers with polarizable aromatic pendant side groups are increasingly being recognized as the materials of the future. Recently it has been pointed out that the axial ordering spontaneously present in nematic and smectic A polymers can be used to enhance field-induced polar ordering by elongating the orientational distribution function along the electric field direction. Depending on the value of the microscopic order parameters <P>₂ and <P>₄, the performance may be improved by a factor of 1 to 5 by using LCPs instead of ordinary amorphous polymers for SHG.^1-4) Interesting results have been obtained for copolyethers prepared by chemical modification of polyepichlorohydrin with classical 4-cyano-4'-hydroxybiphenyl mesogenic group which possesses NLO properties itself.^5-8) These copolyethers afford the opportunity to fine-tune the polymer properties by varying the concentration of the mesogenic side groups. As the concentration is increased, we move from a purely isotropic polymer to a nematic polymer. Spin-coated films have been activated using the corona poling technique and the order parameters <P>₂ have been determined from optical absorption spectra. The second harmonic coefficients d₃₃ and d₃₁ have been measured and compared with different statistical models. In view of the great practical importance, characterization of the wavelength dispersion has been carried out. It agrees well with the two-level approximation model. The dynamics of optical SHG has been investigated. It has been shown that both the presence of LC character in the material and the temperature at which the films are stored below Tg are important in determining the stability of the SH coefficients. A polyacrylate and a polymethacrylate bearing the same 4-cyanobiphenyl-based side groups have also been studied.^7-8) Of particular interest is the fact that the former is nematic while the latter is purely isotropic at rest, the addition of a methyl group to each structural unit of the polyacrylate backbone creating a higher conformational barrier to mesogen packing. Studies of the temporal and thermal characteristics of the poling process have been performed to: •understand and control the poling process with the intention of maximizing poling induced nonlinearity and stability. •elucidate the influence of the polymer backbone, our data including the use of the same mesogenic unit attached to increasing flexible backbones (e.g. polymethacrylate and polyether). •establish if, in the isotropic cases, noticeable axial order can be induced by the poling field, especially when the system is pulled through nematic/isotropic transition by the electric field.     

Nonlinear optical properties of some side chain copolymers based on benzoxazole containing chromophores

Acrylate‐methylmethacrylate copolymers have been synthesized for nonlinear optical applications. Acrylate monomer units are characterized by the presence in the side chain of phenylbenzoxazole groups containing electron donor‐electron acceptor substituents. The phase behavior of all polymers has been investigated by DSC, X‐ray diffraction and polarizing microscopy: two of them exhibit liquid crystalline behavior of smectic type. For four polymers, nonlinear optical properties have been examined by second harmonic generation measurements on thin films (∼ 1 μm thickness) electrically poled by corona discharge. Second order susceptibility coefficients d₃₃ and average relaxation times 〈τ〉, relative to the time stability of the chromophore poling, have been measured. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 603–608, 1999     

Synthesis and nonlinear optical properties of side chain liquid crystalline polymers containing azobenzene push–pull chromophores

Azobenzene monomeric precursors bearing piperazine as donor moiety with different withdrawing groups and derived side chain polymethacrylates have been prepared and characterized. Monomers having terminal cyano or nitro groups, and the corresponding polymers, exhibited smectic A phases. Linear and nonlinear optical properties of every monomer and thin films of the cyano polymer ( pol‐PZ‐CN ) have been also studied. UV‐vis spectroscopy revealed out‐of‐plane orientation in the as prepared films, as confirmed by waveguide refractive index measurements. Moreover, absorption spectra indicated the presence of azo aggregates in these films. The initial molecular arrangement has been modified by applying thermal annealing within the mesophase range and UV‐blue irradiation. Although thermal annealing resulted in a significant amplification of the out‐of‐plane optical anisotropy due to thermotropic self‐organization of side chain azo moieties, irradiation with 440 nm light induced some disruption of aggregates. The nonlinear optical response of Corona poled films has been studied by second harmonic generation measurements, and the influence of the molecular arrangement on the nonlinear d_ij coefficients has been analyzed. The more efficient poling corresponded to preirradiated films. In any case, a noticeable degree of polar order (70% of the initial d₃₃ value) remained for several months after the poling in films kept at RT. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 232–242, 2010     

Morphological alignment of liquid crystalline conducting polyacetylene derivatives

We have synthesized novel liquid crystalline conducting polymers by introducing liquid crystalline group into acetylene monomer and polymerizing them with Ziegler-Natta [Fe(acac)₃ - AlEt₃] and metathesis [M0Cl₅ - Ph₄Sn] catalysts. The liquid crystalline group is composed of a phenylcyclohexyl (PCH) or biphenyl (BP) moiety as a mesogenic core, a trimethylene chain [-(CH₂)₃-] as a spacer, and an alkyl chain (-C_nH_2n+1, n = 2, 3, 5 ∼ 8) as a terminal group. The polymers are abbreviated as PPCHn03A and PBPn03A. All polymers prepared exhibited solubility in organic solvents and smectic liquid crystallinity characterized with fan-shaped texture in polarizing optical microscopy. Phase transitions and the corresponding enthalpy changes were also evaluated by means of differential scanning calorimetry (DSC). Macroscopic alignments of the polymers were performed in the liquid crystalline phase by shear-stress or magnetic force field of 0.7 − 1.0 tesla, which resulted in an enhancement by two orders in electrical conductivity of iodine-doped cast films. Changes of the electronic and geometrical structures of the polymer upon the iodine-doping were elucidated by examining the effective conjugation length of a polyene chain, cis and trans thermal isomerization, and spin distribution of unpaired electrons through ultraviolet / visible (UV-Vis) and electron spin resonance (ESR) measurements.     

Luminescent Iridium-containing liquid crystalline polymers in the side chain

Luminescent liquid crystalline polymers consisting of Iridium attached to polysiloxanes are prepared. 4-Cyanophenyl 4-(allyloxy) benzoate (M₁) and an Iridium complex (Ir-M₂) grafted to poly(methylhydrogeno)siloxane are used for the preparation of the Iridium-containing liquid crystalline polymers. The chemical structures are characterised by Fourier transform infrared spectroscopy and ¹H NMR. The mesomorphic properties and phase behaviour are investigated by differential scanning calorimetry, thermogravimetric analysis, polarising optical microscopy and X-ray diffraction. The polymers containing <1.2 mol% of the Iridium ions reveal reversible mesomorphic phase transition, wide mesophase temperature ranges and high thermal stability. The introduction of the Iridium ions does not change the liquid crystalline state of polymer systems; on the contrary, the polymers are enabled with the luminescent properties. With the Iridium ion contents ranging between 0.3 and 1.2 mol%, luminescent intensity of polymers gradually increased. The temperature dependence of luminescent intensity was studied in the liquid crystalline phase.     

Studies on thermotropic liquid crystalline elastomers. II. Synthesis and properties of liquid crystalline polyester elastomers

Three series of novel thermotropic liquid crystalline polyester elastomers (TLCPEEs) were prepared by direct polycondensation from terephthalic acid, polyols (M_n = 1000 or 2000), and various diols. The structures and thermal properties of the synthesized TLCPEEs were examined by FTIR spectroscopy, differential scanning calorimetry, thermal optical polarized microscopy, thermogravimetric analysis, and wide-angle x-ray diffraction. The effects of kinds and amount of diols and the molecular weight of polyols on the thermal properties of TLCPEEs were studied. By introducing long flexible spacers (PE-1000 or PE-2000) into the polymer main chain, all polymers showed two-phase morphology under the thermal optical microscopic observation. All of the synthesized polymers, except polymer P1-BPA60 and P2-BPA60, which were prepared from BPA, exhibited thermotropic liquid crystalline properties that were in the smectic phase. © 1995 John Wiley & Sons, Inc.     

Synthesis and second-order nonlinear optical properties of a crosslinkable functionalized hyperbranched polymer

A new implementation of copper-free thermal Huisgen 1,3-dipolar crosslinking reaction into a high T_g hyperbranched polyimide polymer in order to stabilize the electro-optic (EO) activity of second-order non linear materials is reported. Towards this goal, two different synthetic approaches were explored. The first strategy is based on the post-functionalization of the polymer with mixtures of DR1 azido derivative and propargylic alcohol, whereas, the second consists in the preparation of two complementary functionalized hyperbranched polymers that are mixed just before the preparation of films. Materials exhibit good second-order nonlinear optical coefficients (d₃₃) close to 30 pm/V at the fundamental wavelength of 1064 nm. Moreover, the thermal stability of the NLO properties of these materials reaches temperatures as high as 150 °C, and probably higher. This represents the highest thermal stability of crosslinkable EO polymers based on the crosslinking Huisgen reaction.     

New PVK‐based nonlinear optical polymers: Enhanced nonlinearity and improved transparency

A series of poly(vinylcarbazole)‐based polymers containing sulfonyl‐based nonlinear optical chromophores as the side chains were prepared conveniently through a postfunctionalization approach. In the polymers, the subtle structure of the chromophore moieties could be easily modified by the introduction of different isolation group, to adjust the property of the resultant polymers. The polymers exhibited good optical transparency, besides their good processability and thermal stability. The poled polymer films exhibited large second harmonic generation (SHG) coefficients of d₃₃ values (up to 28.6 pm/V) with excellent thermal stability (about 90% of the maximal SHG coefficients remain at ～ 110 °C). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2983–2993, 2008     

Effect of pendant group on the second-order optical nonlinearity of sol–gel films

A series of organically modified sol–gel films with various acceptor groups were prepared and characterized. All the chromophores exhibit much larger microscopic optical nonlinearity compared with the classical chromophore DR1 in solvatochromic measurement. Using in situ second harmonic generation (SHG) technique, the optimal poling temperatures (T _opt) for sol–gel films were obtained. The second harmonic coefficients (d ₃₃) of hybrid films at the wavelength of 1,064 nm were in the range of 50.1–70.3 pm/V after corona poling under their T _opt. The NLO stabilities of these poled films were also investigated by tracing the d ₃₃ value as a function of temperature and time. One of the hybrid films, which was prepared from chromophore 2,4-dinitro-4′-(N,N-dihydroxyethyl) aminoazobenzene exhibited a combination of large optical nonlinearity and high NLO stability. Furthermore, the effects of molecular structure on the NLO property and thermal stability of the hybrid films were also discussed.     

Ferrocene‐based organophosphorus liquid–crystalline polymers: Synthesis and characterization

Ferrocene‐containing polyphosphate and phosphonate esters were synthesized by the solution polycondensation method. The structure of the polymers was confirmed using various spectroscopic techniques. The formation of two types of chain blocks was confirmed by ³¹P NMR spectroscopy. Hot stage optical polarized microscope (HOPM) analysis revealed that all the polymers have a liquid–crystalline property. The char yields of the synthesized similar polymers were much higher than those of nonphosphorus polymers already reported in the literature. DSC analysis confirmed our predictions over the liquid–crystalline property, glass‐transition temperature, isotropization temperature, and thermal stability of the polymers. The effects of substitution on the side chain, structure of the liquid‐–crystalline phase, and thermal stability of the polymers have also been discussed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2396–2403, 2001     

Synthesis and characterisation of polymethacrylates containing para-, meta- and ortho-monosubstituted azobenzene moieties in the side chain

Three sets of novel side-chain liquid crystalline polymers with monosubstituted azobenzene moieties in the side-chain have been studied. These are poly(p-(4′-methoxy-4-oxyhexyloxy azobenzene) benzyl methacrylate) (PPHABM), poly(m-(4′-methoxy-4-oxyhexyloxy azobenzene) benzyl methacrylate) (PMHABM) and poly(o-(4′-methoxy-4-oxyhexyloxy azobenzene) benzyl methacrylate) (POHABM). The chemical structure of the monomers was confirmed by ¹H NMR, ¹³C NMR spectroscopy and elemental analysis. The structural characterisation of the polymers was performed by ¹H NMR spectroscopy and gel permeation chromatography, and their phase behaviour and liquid crystalline properties were studied using differential scanning calorimetry, polarised optical microscopy and wide-angle X-ray diffraction. The results show that the transitional behaviour of side-chain liquid crystalline polymers containing monosubstituted azobenzene moieties depends strongly on the position of the substituent on the azobenzene moiety; for example, the ortho-monosubstituted polymers do not form liquid crystalline phases, but all the para- and meta-monosubstituted polymers exhibit a smectic A phase. Furthermore, the glass transition temperature (T_g ) of the polymers decreases in the order, para > meta > ortho. For the PPHABM and PMHABM polymers the isotropic temperature (T_i ) and liquid crystalline range (ΔT, from T_g to T_i ) are found to be in the order, para > meta, although it is surprising that the associated enthalpy changes in these polymers is the opposite order, meta > para.     

Synthesis and characterization of fluorinated benzoxazole polymers with high Tg and low dielectric constant

Next generation microelectronic packaging requirements are driving the need to produce increasingly lower dielectric constant materials while maintaining high thermal stability and ease of processing. Efforts have focused on the synthesis and analysis of new polymers with the goals of high thermal stability [degradation temperature (T_d) > 400 °C, low glass‐transition temperature (T_g) > 350 °C], low water uptake (<1%), solubility in selected organic solvents, dielectric constant less than 2.5, and low thermal expansion coefficient. These stringent combined goals have been largely achieved with flexible aromatic benzoxazole polymers. Intramolecular hydrogen bonding between pendant hydroxyl groups and the double‐bond nitrogen of the benzoxazole has been exploited to increase the polymer T_g, whereas the incorporation of perfluoroisopropyl units effectively decreases the dielectric constant. Out‐of‐plane impedance measurements on films of materials in this family (38–134 μm thick) have resulted in typical dielectric values of 2.1–2.5 at 1 MHz, depending on copolymer ratios and functionalizations. Results have been correlated with optical waveguide measurements of films 4‐μm thick to determine film anisotropy and the high‐frequency dielectric constant, and have been corroborated by in‐plane interdigitated electrode dielectric measurements on samples 0.75 μm thick. Candidate materials exhibited extremely low water uptake (0.2%) even after submersion in boiling water for several days. Dynamic mechanical analysis of the polymers enabled the determination of the influence of intermolecular hydrogen bonding on the T_g and loss tangent magnitude. Finally, the coefficient of thermal expansion has been examined and correlated with copolymer constitution. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1991–2003, 2000     

Design and synthesis of a thermally stable second‐order nonlinear optical chromophore and its poled polymers

A multiple charge‐transfer second‐order nonlinear optical (NLO) chromophore 2,3‐bis(4‐aminophenyl)‐5,6‐dicyanopyrazine (BAPDCP) was successfully designed and synthesized. It was characterized by ¹H NMR, mass spectrometry, Fourier transform infrared spectroscopy, and elemental analysis. The first hyperpolarizability β of BAPDCP was measured with the Hyper–Rayleigh scattering technique, which was 123.5 × 10^?30 esu. The donor‐embedded prepolyimide and prepolyurea were also synthesized by a polyaddition reaction. Thermogravimetric analysis and differential scanning calorimetry demonstrated that either the chromophore or the polymers have fine thermal stability. The thin films of prepolymers were prepared by coating on ITO glass substrate and poled by corona poling at elevating temperature. The second‐order NLO coefficients d₃₃ of the films were measured by in situ second‐harmonic generation measurements. The d₃₃ were deduced as 27.7 and 16.5 pm/V for polyurea and polyimide at 1064 nm fundamental wavelength, respectively. The onset depoling temperature of the polyimide and polyurea were both as high as 200 °C. To understand the temperature effect to the orientation thermal stability of polyimide, two films were treated at different final poling temperatures. The depoling experimental results showed that the orientation stability is higher, as raising the final treated temperature but the d₃₃ value are almost similar. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2846–2853, 2003     

Effect of fluorinated nematic mesogens on phase behaviors and optical properties of chiral liquid crystalline polysiloxanes

A series of new chiral side-chain liquid crystalline polymers (P₁–P₇) have been synthesized with poly(methylhydrogeno)siloxane, two chiral liquid crystalline monomers, cholesteryl-4-allyloxybenzoate (M₁) and cholesteryl 4-(10-undecylen-1-yloxy) benzoate (M₂), and a nematic liquid crystalline monomer, 4-(trifluoromethyl)phenyl 4-(undec-10-enoyloxy)benzoate (M₃). The chemical structures and liquid crystalline properties of the synthesized polymers have been investigated by FTIR, ¹H-NMR, differential scanning calorimetry (DSC), polarizing optical microscopy (POM), thermogravimetric analysis (TGA), and X-ray diffraction (XRD). All chiral polymers show wide mesophase temperature ranges and a high thermal stability with decomposition temperatures (T _d) at 5 % weight loss greater than 300 °C. P₁–P₄ display a single cholesteric phase, but P₅–P₇ containing more fluorinated units show a smectic A (SA) phase besides a cholesteric phase. The optical properties of the polymers have been characterized by circular polarization spectra and optical rotation analysis. The cholesteric polymers P₃ and P₄ exhibit different colors at room temperature, and the color can remain over 24 months. The maximum reflection bands of polymers P₁–P₄ shift to long wavelength with increasing the content of M₃ in the polymer systems. For P₅–P₇, the reflection wavelengths change sharply around the temperature of the SA–Ch phase transition. The specific rotation value of P₂ smoothly decreases from ?8.2° to ?0.29° when it is heated, but the specific rotation value of polymer P₇ changes from negative value to positive value on heating cycle. The optical properties of the polymers offer tremendous potential for various optical applications.     

Thermal conductivity and thermal expansivity of thermotropic liquid crystalline polymers

The thermal conductivity and thermal expansivity of a thermotropic liquid crystalline copolyesteramide with draw ratio λ from 1.3 to 15 have been measured parallel and perpendicular to the draw direction from 120 to 430 K. The sharp rise in the axial thermal conductivity K_par; and the drastic drop in the axial expansivity α_∥ at low λ, and the saturation of these two quantities at λ > 4 arise from the corresponding increase in the degree of chain orientation revealed by wide-angle x-ray diffraction. In the transverse direction, the thermal conductivity and expansivity exhibit the opposite trends but the changes are relatively small. The draw ratio dependences of the thermal conductivity and expansivity agree reasonably with the predictions of the aggregate model. At high orientation, K_par; of the copolyesteramide is slightly higher than that of polypropylene but one order of magnitude lower than that of polyethylene. In common with other highly oriented polymers such as the lyotropic liquid crystalline polymer, Kevlar 49, and flexible chain polymer, polyethylene, α_par; of the copolyesteramide is negative, with a room temperature value differing from those of Kevlar 49 and polyethylene by less than 50%. Both the axial and transverse expansivity show transitions at about 390 and 270 K, which are associated with large-scale segmental motions of the chains and local motions of the naphthalene units, respectively. ©1995 John Wiley & Sons, Inc.     

Molecular design, synthesis and electro-optic properties of novel Y-type polyurethanes with high thermal stability of second harmonic generation

2,4-Di-2^′-hydroxyethoxy)benzylidenemalononitrile (3) was prepared and condensed with 2,4-toluenediisocyanate and 3,3^′-dimethoxy-4,4^′-biphenylenediisocyanate to yield unprecedented novel Y-type polyurethanes (4-5) containing 2,4-dioxybenzylidenemalononitrile group as a nonlinear optical (NLO) chromophore, which constitutes a part of the polymer backbone. The resulting polyurethanes 4-5 were soluble in common organic solvents such as acetone and DMF. Polymers 4-5 showed a thermal stability up to 260 °C from thermogravimetric analysis (TGA) with differential scanning calorimetry (DSC) giving T_g values around 143-156 °C. The approximate lengths of aligned NLO-chromophores estimated from AFM images of poled polymer films were about 10 nm. The SHG coefficients (d₃₃) of poled polymer films were around 7.4 × 10⁻⁹ esu. These Poled polymers exhibited a greater thermal stability of dipole alignment even at 10 °C higher than T_g, and no SHG decay was observed below 155 °C due to the partial main chain character of the polymer structure and extensive hydrogen bonds between urethane linkage, which is acceptable for NLO device applications.     

Novel diacetylene-containing polymers for second order NLO applications: effect of main chains and structure property relationships

In order to obtain polymers having high second order nonlinear optical (NLO) response, various novel polymers that contain polar dye molecules in side chains and diacetylenic groups in the main chains were synthesized, and their second order NLO properties were studied. Some of these polymers consisting of para-benzoate and para-cinnamate main chains, showed extremely high NLO coefficients, d₃₃ of 200 - 350 pm/V, and the corresponding meta polymers showed much inferior NLO coefficients. The polymers having aliphatic main chains had very little NLO response probably because of their low glass transition temperatures and flexibility of main chains. The high SHG responses of these polymers are attributed to their facile orientation of both chromophores and main chains. In the case of para-polymers, the main chain orientation of alkoxybenzoate and cinnamate along the chromophore is thought to be a reason for their high NLO coefficients.     

Synthesis and photophysical properties of soluble polyimides and polyquinazolones containing side-chain chalcones or azo chromophores

Soluble aromatic and carboxyl- and hydroxyl-containing polyimides, mixed polyimides, and polyquinazolones of various chemical structures, as well as a series of new dicyanoazobenzene chromophores, are synthesized. From 20 to 80 mol % of chromophore groups are incorporated into side chains of the polymers. The thermal, photosensitive, and nonlinear optical properties (second-harmonic generation) of the chromophore-containing polymers are investigated. The polymers with covalently attached groups of the dye DR-13 or azo-derivatives of 4-phthalonitrile demonstrate the highest nonlinearity. The T _g values of the polyimides vary from 165 to 215°C; their temperatures corresponding to 5% weight loss lie in the range 290–350°C; and the measured coefficients of second-harmonic generation, d ₃₃, for a number of polarized films based on chromophore-containing polymers attain several tens of picometers per volt. The incorporation of chromophore groups into the side chains of the polymers causes an increase in the photosensitivity of polyimides by an order of magnitude relative to that of the parent polymers (S _0.1 = (3?4) × 10⁵ cm²/J in the range of dye absorption).     

Surface study of ladderlike polyepoxysiloxanes

By using the two‐liquid geometric method and the three‐liquid acid‐base method, we are the first to determine the surface tensions of ladderlike polyepoxysiloxanes by the measurement of contact angles on thin films. Three kinds of ladderlike polymers have been synthesized: A C (which has the alkyl group and the epoxy group graft to the ladderlike polysilsesquioxane chain), A C P (which has the alkyl group, phenyl group, and epoxy group graft to the ladderlike chain), and A P (which has the phenyl group and epoxy group in the ladderlike side chain). The results showed that when different liquids and different theories are chosen to determine the surface energies, there are some minor differences in the values but a similar trend is still exhibited. The surface energies of these three polymers are in the following order of γ_{SA C} < γ_{SA C P} < γ_{SA P}. Interestingly, the surface energy increases for these polymers are mainly from the nonpolar part of the polyepoxysiloxanes. XPS surface analysis indicated that the Si and O ratios of these polymers at the air‐polymer interface were in the order of A C > A C P > A P, suggesting Si atoms were more likely to migrate to the polymer surface and the bulky effect of the phenyl groups could also interfere with the migration of the Si atoms. As a result, Si and O ratio at the interface determines the order of apparent surface energy for these three polymers. Experimental data also reflect that there are differences between the ladderlike polyepoxysiloxanes and the commercially available linear polysiloxanes. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 138–147, 2000     

Synthesis and characterization of copolymaleimides containing 4‐cyanobiphenyl‐based side groups for nonlinear optical applications

We report the synthesis of a nematic copolymer, P(CBMS‐co‐M₃), prepared by free radical polymerization of an equimolecular mixture of p‐(4‐cyanobiphenyl‐4′‐yloxy)methylstyrene (CBMS) and N‐[3‐(4‐cyanobiphenyl‐4′‐yloxy)propyl]maleimide (M₃) and two isotropic alternating copolymers, P(S‐alt‐M_n) (n = 3,6) prepared by chemical modification of poly(styrene‐alt‐maleimide), P(S‐alt‐M), by n‐(4‐cyanobiphenyl‐4′‐yloxy)alkan‐1‐ol. These copolymaleimides were characterized by NMR, DSC, and optical microscopy. Some corona poling experiments were performed and the second harmonic coefficients d₃₁ and d₃₃ were measured. It was shown that one can gain in net polar ordering by starting with a liquid crystalline system. The ratio d₃₃/d₃₁ was much larger than 3, in agreement with the molecular statistical models for electric field poling of liquid crystals. At ambient conditions, changes of d₃₃ and d₃₁ are 15% over 325 days. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 513–524, 1999