EP0595921A1 - Preparation of nonlinear optical elements - Google Patents

Abstract

A method of producing shaped elements for use as nonlinear optical elements, comprising reacting a polyvalent polymer with a complementary monovalent compound containing a polar dye moiety while the mixture forms the final shape of the element. The final polymer contains side chains that include the polar dye moieties and can optionally be cross-linked. Also disclosed is a cross-linked polymer comprising side chains containing polar dye moieties.

Description

TITLE

PREPARATION OF NONLINEAR OPTICAL ELEMENTS

FIELD OF THE INVENTION This invention concerns the production of a shaped part useful as a nonlinear optical element by reaction of a monofunctional dye containing molecule with a polyfunctional polymer while the mixture is in the final shape of the nonlinear optical element. The resulting shaped part may also be poled and/or simultaneously

(with the above reaction) crosslinked. Also disclosed is a crosslinked polymer having side chains containing dye moieties.

BACKG OUND QF THE INVENTION Organic molecules having large nonlinear polarizabilities have been recognized as potentially useful as components of the optical elements in optical frequency converters and in electrooptic devices. In order to create organic materials exhibiting the large second order optical susceptibilities essential to nonlinear optic applications, the molecules must be constructively arrayed in a noncentrosymmetric configuration. Such molecules have been crystallized in a noncentrosymmetric space group, but this method does not work for all potentially useful molecules and the resulting shape and properties are limited by the very nature of a crystal.

A number of other methods for noncentro- sym etrically arranging the molecules to optimize the nonlinear properties of the resulting organic material have been used. For example, strong DC electric poling fields have been applied to polar dye molecules in semi¬ fluid polymeric or glassy matrices in order to align the molecules noncentrosymmetrically. The matrices are then rigidified, while still under the influence of the externally applied DC field, to "lock" the at least partially aligned dye molecules in place. In still another approach polar dyes are attached directly to polymeric backbones which are similarly treated to lock the polar dyes in biased alignment. Furthermore, the polymer can dilute the effective nonlinearity, as it is often difficult to get more than 10 to 20 percent of nonlinear molecules into the polymer reagent.

Such polar dyes attached to the backbone of the polymer (herein sometimes referred to as "comb" polymer), are known in the art, see for example J. S. Schildkraut, Appl. Phys. Lett., vol. 58, p. 340-342 (1991) . These polymers then have been formed into the shapes of nonlinear optical elements (and simultaneously or later poled) , such as films, for example by spin coating of solutions or by melt forming.

However, for many such desirable comb polymers, fabrication into the desired shape is difficult or impossible because the polymer is insoluble and/or not sufficiently thermally stable. This arises from the use of certain dye moieties and/or a large number of dye moieties in the polymer side chains. It is desirable to have as many dye moieties in the polymer as possible to give a stronger nonlinear optical effect. It is an object of this invention to provide nonlinear optical elements of the correct shape, by forming the final nonlinear optical element shape before or approximately simultaneous with the attachment of the dye containing side chains to the polymer backbone. P. S. Ramanujam in WO 88/02131 incorporates 2- methyl-4-nitroaniline (MNA) into a two-component curable epoxy resin. It is not stated that the MNA, or any other dye, is incorporated into the polymer as a side chain. Eich et al., J. Appln. Phys. 66(7), October 1, 1989, pp. 3241-3247, discloses the preparation of nonlinear optically active crosslinked polymer networks from the reaction of diepoxides, with and without nonlinear optic (NLO) dye moieties, and NLO active di- and tri-functional amines. Hubbard et al.. Chemistry of Materials, Volume 1, Number 2, March/April 1989, pp. 167-169, disclose crosslinked epoxy polymer reagent networks containing dispersed NLO dyes similar to those disclosed by Eich et al. In Eich, et al., the dye molecules become part of the polymer network, but the dye molecules are themselves difunctional, so become part of the polymer network, not merely side chains. In Hubbard, the dye molecules are merely "dissolved" in the polymer network, not covalently bound to the polymer.

SUMMARY OF THE INVENTION

This invention concerns a process for the production of a shaped part, comprising: (a) reacting (i) a polyfunctional polymer containing active groups; with (ii) a compound containing a polar dye moiety and one reactive group; said reacting forming a polymer having side chains containing one or more polar dye moieties; and (b) shaping the part; wherein said shaping is carried out before or substantially simultaneously with said reacting such that when substantial reacting occurs the mixture of said polyfunctional polymer and said compound is substantially in the final shape of the shaped part.

DETAILED DESCRIPTION OF THE INVENTION In order to form the nonlinear optical element of the present invention, it is necessary to form a mixture of a polyfunctional polymer containing active groups (sometimes herein abbreviated PP) and a compound containing a polar dye moiety and one reactive group(sometimes herein abbreviated CCPD) . In order to form the nonlinear optical element, the PP and CCPD must contain groups that are complimentary to each other, that is, the groups can react with each other to form the comb polymer. For the sake of clarity, such groups attached to the PP will be referred to herein as "active groups", and such groups attached to the CCPD will be referred to herein as "reactive groups."

By a "side chain" herein is meant a group that is not part of a main polymer chain or a crosslink. Thus side chains are attached to the polymer (crosslinked or uncrosslinked) by only one bond. A group bound to the polymer or polymer network by more than one bond is said herein to be "within" the main chain of polymer or the polymer network, and are not in side chains. More than one type of active group and/or reactive group may be present in the mixture, but if this is the case, each of the active groups must not react with any of the other active groups, and each of the reactive groups must not react with any of the other reactive groups. However, as mentioned above, the active and reactive groups should react with each other. Typical complimentary groups are shown in the two columns below, the groups in column (b) being complimentary to those in column (a) .

________ hydroxyl, carboxyl hydroxy1, thiol hydroxy hydroxy

hydroxyl ¹Primary and secondary amino only. ²Water needed for the reaction of these groups, In order to pick a set of complimentary active and reactive groups, one would choose a group from column (a) and a group from column (b) , on the same line. The choice of active and reactive groups from columns (a) and (b) would depend primarily upon the availability or difficulty in synthesizing the particular polymer reagent and crosslinking agent with those groups. Useful examples of compounds having complementary groups are described below. It is preferred if the active and reactive groups are chosen so that when they react no small molecules are produced. For example, hydrolysis and condensation of the alkoxysilyl groups will produce an alcohol, which is undesirable, but reaction of an isocyanate with an amino group produces no small molecule. Preferred active or reactive groups are epoxy and isocyanate and their complimentary groups, and an especially preferred active or reactive group is isocyanate. The PP used in the present invention should have a degree of polymerization of at least about 5. By degree of polymerization is meant the average number of monomer units in the PP molecule. Although there is no upper limit on the degree of polymerization from a theoretical standpoint, practical considerations, such as the ability to form shapes and mix the PP with the CCPD, dictate preferred upper limits on the degree of polymerization. Therefore it is preferred if the degree of polymerization of the PP is about 10 to about 3,000, more preferably about 50 to about 1,000.

The PP contains two or more active groups. The active groups may have been present in some or all of the monomers used to form the polymer reagent, or may be formed on the polymer reagent by chemical modification after the monomers have been polymerized. The PP may be formed from appropriate monomers by methods well known to those skilled in the art, for example addition or condensation polymerization. Addition polymers, particularly vinyl addition polymers, are preferred, since active groups are relatively easy to introduce into such polymers as part of the monomer units. The polymers may be homopolymers or copolymers. It is preferred that the monomers be chosen so that the resulting polymer does not contain a substantial crystalline fraction, i.e., is amorphous. A minor amount of crystallinity can be tolerated without loss of desirable nonlinear optical properties. In general, the presence of significant crystallinity in the polymer can cause a reduction in efficiency. For example, crystallinity can cause increased scattering of the incident radiation, which can significantly decrease the efficiency of any optical device utilizing these crosslinked polymers. Furthermore, depending on the amount, location and type of crystallinity in the crosslinked polymer, SHG (second harmonic generation) can be greatly diminished. If the polymer reagents are copolymers, not all of the monomeric units need contain active groups, although it is preferred if as high a proportion as possible do. This high proportion of active groups is desirable because a relatively high proportion of CCPD contributes to stronger nonlinear optical properties.

Preferred vinylic monomers from which the polymer reagent is made include acrylic monomers and styrene and substituted styrenes. Particularly preferred acrylic monomers are methacrylates, which give polymer reagents with higher glass transition temperatures, which is believed to be advantageous for the stability of the NLO effect. Monomers containing functional groups which are useful in the polymer reagent, include but are not limited to, maleic anhydride, acryloyl chloride, methacryloyl chloride, 2-isocyanatoethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, 4-iso- cyanatostyrene, 3-(2-isocyanato-2-propyl)-α-methyl- styrene, 2-hydroxyethyl methacrylate, 4-aminostyrene, methyacrylic acid, and 3-trimethoxysilylpropyl methacrylate. Preferred functional monomers are acryloyl chloride, methacryloyl chloride, 2-isocyanatoethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, 4-isocyanatostyrene and 3-(l-iso- cyanato-2-propyl)-α-methylstyrene. Monomers not containing functional groups include, but are not limited to, methyl methacrylate, styrene, 4-methyl- styrene, cyclohexyl methacrylate, ethyl acrylate, and phenyl methacrylate. Preferred nonfunctional monomers are methyl methacrylate and styrene.

The CCPD contains a dye moiety. The dye moiety useful in the practice of this invention should have a molecular hyperpolarizability, beta, of greater than about 10^*"³- esu (electrostatic units) measured by conventional EFISH methods, as described in L. T. Cheng, et al., SPIE, vol. 147, p. 61-72 (1989) which is incorporated herein by reference. Dye moieties often have three subunits, arranged A-E-D. A is an electron acceptor group such as cyano, nitro, perfluoro- alkylsulfonyl, D is an electron donor group such as amino or alkoxy, and E is a group having a conjugated pi-bond system. These groups are arranged within the dye moiety so that it has noncentrosymmetric molecular dipoles having an electron donor group linked through a pi-bonding system to an electron acceptor group. Such dye moieties (either as compounds in their own right, or as parts of compounds) , and their structural requirements, are well known to those skilled in the art, see for example L. T. Cheng, et al., supra. Examples of CCPDs useful herein include, but are not limited to, 4-(N-2-hydroxyethyl-N-ethylamino)-l-(2,2- dicyanoethenyl)benzene, 4-(N-2-hydroxyethyl-N- ethylamino)-4'-nitroazobenzene (Disperse Red 1), 4-(2- hydroxyethoxy)-4'-nitrostilbene, 4-{4'-[N-(2-methyl-3- hydroxypropyl)-N-methyl]biphenylyl} (hepta-fluoro- propyl)sulfone, [4-(2-hydroxymethyl-l-pyrrolidinyl)- phenyl] (tridecafluorohexyl)sulfone, 3-nitrophenyl- isocyanate, ethyl 4-isocyanatobenzoate, and 4- dicyanomethylene-2-methyl-6-[4-(N-2-hydroxyethy1-N- ethyla ino)-α-styryl]-4H-pyran.

The two components of the mixture, the PP and the CCPD, may be mixed by conventional means, e.g., stirring to mix two liquids or dissolve one solid in a liquid. Heat may be used if necessary to effect mixing, however, care must be taken to avoid much reaction until a homogeneous mixture (solution) and essentially the final part shape is obtained. The reactivity can be adjusted by the selection of the active and reactive groups, and the molecules which they are part of. If reaction is slow, a catalyst for the reaction may be added, provided it does not substantially affect the properties of the resulting nonlinear optical element. Such catalysts are well known to those skilled in the art for various active and reactive groups, including those enumerated above, and the chemical reactions are also well known to those skilled in the art.

The mixture described herein is used to produce a nonlinear optical element in which a substantial proportion of the dye moieties are in biased alignment resulting in a nonlinear optical element having desirable properties. Simultaneous with or after the reaction to form the comb polymer, an electric field may be applied (poling) . This should be done when the dye moieties in the mixture or comb polymer exhibit significant molecular mobility. In cases where the mixture or comb polymer are glasses, this point is often about at or above the glass transition temperature (Tg) . Thus it is preferred to pole the nonlinear optical element about at or above Tg. It is also preferred to continue to apply the electric field until the nonlinear optical element is cooled below Tg to "lock in" the alignment of the dye moieties.

By the term "substantially in the final shape" is meant herein that the nonlinear optical element shall be in its approximate final shape at the time substantial reaction to form the comb polymer is taking place. This shape may be any useful shape, and shapes useful for nonlinear optical devices, such as a film, are preferred. It will be understood by those skilled in the art that during the reaction small changes in the dimensions of the element may take place. In addition, after the nonlinear optical element is formed, it may be mechanically trimmed or shaped. That is, although the polymer molecules will not be forced to move substantially with respect to one another to change the shape, the part, for example a film, may be trimmed or made into several elements by cutting. The elements may also be ground, polished, etc. to achieve their final configuration. Simultaneous with the reaction to form the comb polymer, that is while the dye containing side chains are being bound to the polyfunctional polymer, the polymer may be crosslinked by molecules (crosslinking agents) containing two or more reactive groups, but which do not contain dye moieties.

Crosslinking may be desirable to make the polymers within the nonlinear optical element even more rigid, and hence less susceptible to the loss of SHG signal due to movement of the dye moieties after poling. The reaction of the crosslinking agent with the polyfunctional polymer may be controlled in the same manner as described above for the reaction of active and reactive groups. Preferred reactive groups for the crosslinking agent are the same as for the dye containing compound. Preferred crosslinking agents for polymers containing isocyanate active groups are diols containing 8 or less carbon atoms, and especially preferred diols are ethylene glycol, 1,3-propanediol, 1,3-butanediol, and 1,4-butanediol. An electric field for poling is commonly created in one of two ways, corona poling or electrode poling.

In electrode poling the electric field is created between two closely spaced electrodes. Depending on the desired sample configuration, these electrodes can either be in the plane of a thin film, in which case the field is primarily parallel to the surface of the sample; or it can be in a plane above and below the sample, in which case the field is perpendicular to the sample surface. The latter configuration has the advantage of generating high fields over a large area, but has the disadvantage for frequency doubling of requiring that the electrodes are transparent (transparency required only to measure transmitted SHG light) and that the sample is tilted with respect to the input beam. This latter requirement is necessary so that a component of the fundamental beam's electric field can be parallel to the poling direction.

Electrode poling has several disadvantages, particularly when surveying a large number of new materials where the thin film quality and characteristics have not been optimized. Because of the high fields involved, electrochemistry can take place at the electrodes, thereby altering material properties. Also microscopic defects can lead to electrical breakdown at potentials many times smaller than a defect-free film could sustain. Such a breakdown will typically ruin a sample since the entire charge contained on the electrodes will flow through a small area of the sample causing thermal damage not only to the sample but also to the electrodes.

Corona poling avoids these disadvantages. A corona discharge is used to create the electric field by depositing charge on a thin film sample which has been coated on a conductive substrate. Corona poling eliminates the high voltage electrode. Since there is no conductive electrode to carry charge to a defect, the catastrophic damage associated with having a conductive point defect is also eliminated. This technique does, however, have the limitations of requiring a transparent (transparency required only to measure transmitted SHG light) electrode and a tilted sample. In addition, since a corona discharge is a current limited source, modest sample conductivity will cause a reduction in the maximum field which can be generated. For a discussion of corona poling, see, e.g., K. D. Singer et al., "Electro-optic phase modulation and optical second harmonic generation in corona-poled polymer films", Appl. Phys. Lett. 53(19) pp. 1800-1802 (1988).

A preferred form of nonlinear optical element is a film. Nonlinear optical films can be produced by spin coating e.g., depositing a solution of the mixture on the center of rotation of a usually flat substrate, whereby the solution spreads out over the substrate, and the solvent is evaporated, leaving the mixture in the form of a film, and then reacting the spin coated film. The nonlinear optical elements of this invention are considered particularly useful because of their high concentration of nonlinear optically active molecules, their capability of being formed into large area thin films, and their high orientational stability. Preferred film thickness can vary according to use. Typically film thickness is within the range of 0.5 μ - 2 μm.

Nonlinear optical elements can be provided in other forms as well (e.g., a solid block of polymer could be formed into an electrooptic modulator or a frequency converter using conventional techniques known in the art for single crystals) and poled polymers in other forms are also included within this invention. The nonlinear optical elements of this invention transform electromagnetic radiation (e.g., by changing the frequency and/or polarization of the radiation) . Generally, the nonlinear optical element is used for transforming electromagnetic radiation by including it within an optical device. A device for transforming electromagnetic radiation using a nonlinear optical element is described in U.S. Patent No. 4,909,964. The present invention may be used in such a device.

A conventional nonlinear optical device disclosed in U.S. Patent No. 4,909,964 comprises means to direct at least one incident beam of electromagnetic radiation into an element. The element has nonlinear optical properties whereby electromagnetic radiation emerging from the element contains at least one frequency different from the frequency of any incident beam of radiation. The different frequency is an even multiple of the frequency of one incident beam of electromagnetic radiation.

Preferably, the emerging radiation of a different frequency is doubled (second-order) (SHG) . Preferably, the electromagnetic radiation is radiation from one of a number of common lasers, such as Nd-YAG, Raman-shifted Nd-YAG, Nd-YLF or Nd-glass, semiconductor diode, Er-Glass, Ti-Sapphire, dye, and Ar or Kr ion, or radiation shifted to other frequencies by nonlinear processes. For example, polarized light of wavelength 1.06 μ from an Nd-YAG laser is incident on the optical element along the optical path. A lens focuses the light into the optical element. Light emerging from the optical element is collimated by a similar lens and passed through a filter adapted to remove light of wavelength 1.06 μ while passing light of wavelength 0.53 μ.

As disclosed in U.S. Patent No. 4,909,964 (incorporated herein by reference), one conventional electro-optic modulator comprises means to direct a coherent beam into an optical element, and means to apply an electric field to the element in a direction to modify the transmission property of the beam. For example, in an electro-optic modulator comprising an optical element, a pair of electrodes is attached to the upper and lower surfaces of the element, across which a modulating electric field is applied from a conventional voltage source. The optical element is placed between two polarizers. A light beam (such as that from a

Nd-YAG laser) is polarized by a polarizer, focused on the optical element and propagated therethrough, and subjected to modulation by the electric field. The modulated light beam is led out through an analyzer polarizer. Linearly polarized light traversing the optical element is rendered elliptically polarized by action of the applied modulating voltage. The anlayzer polarizer renders the polarization linear again. Application of the modulating voltage alters the birefringence of the optical element and consequently the ellipticity impressed on the beam. The analyzer polarizer then passes a greater or lesser fraction of the light beam as more or less of the elliptically polarized light projects onto its nonblocking polarization direction. It will be further apparent to those skilled in the art that the optical elements formed by the poled polymers of the present invention are useful in this and other devices utilizing their nonlinear properties, such as devices utilizing the electro-optic effect.

In the Examples and Experiments, the following abbreviations are used:

EtOH - ethanol ICEM - 2-isocyanatoethyl methacrylate

ICS - 4-isocyanatostyrene

MMA - methyl methacrylate mR - molar ratio

Mw - peak average molecular weight NLO - nonlinear optical

SHG - second harmonic generation

THF - tetrahydrofuran

In the Examples, the poling apparatus consists of a sample holder constructed so that the sample normal is 45° to the beam direction. The laser beam is polarized so that the electric vector is in the plane defined by the sample normal and the beam. Heaters are incorporated into the sample holder so that the temperature of the sample can be maintained anywhere in the temperature range from room temperature to 200°C. A standard corona charging unit from a xerographic copy machine is positioned over the sample to apply an electric field. Appropriate holes are cut in the sample holder and the corona charging unit to allow both the fundamental beam and any second harmonic light to pass through the sample and be detected.

In some o the following Examples, certain compounds containing a polar dye moiety and one reactive group (an "NLO dye" below) are used. Their designations are given below and these designations are used in the Examples and Experiments.

Experiment 1 Procedure A: Preparation of Homopolymers of Glycidyl Acrylate and Glycidyl Methacrylate

Into a 100 ml round bottom flask containing a magnetic stirrer and fitted with an reflux condenser, thermometer and nitrogen bubbler were placed 0.05 g Vazo-64 (a,a'-azobis(isobutyronitrile) ) initiator, and 40 ml freshly distilled sodium dried THF and 10 ml of either glycidyl acrylate or glycidyl methacrylate. The rapidly stirred solution was then heated to 55°C for 48 hours using an oil bath for maintaining uniform temperature control. After cooling, the polymeric products were transferred to 60 ml serum bottles, flushed with nitrogen, sealed and stored until ready for use. Samples were removed by syringe under positive nitrogen pressure and added to solutions containing reactive NLO active dyes just before spin-coating onto conductive substrates as described in the Examples. Bottles were resealed under nitrogen to retain an anhydrous inert atmosphere.

Procedure B: Preparation of Polyhydroxystyrene This material is commerically available from Polysciences, Inc. (Stock #6527, 18979, 18980)

Procedure C: Preparation of Polyisocyanatostyrene and Styrene-Isocyanatostyrene (S-ICS) Copolymers

Step 1

Into a three necked round bottom flask fitted with a reflux condenser, bubblers to monitor passage of nitrogen and reagent gasses, a mechanical stirrer, and a gas addition tube were placed toluene that had been dried over molecular sieves, styrene, and p-aminostyrene in amounts described in Table I-C-l. Hydrogen chloride gas was then passed into the mixture while stirring until the mixture became saturated, as evidenced by comparing the rate of gas evolution from the reactor to the input rate. Off-gas was trapped using concentrated sodium hydroxide. The reaction temperature was increased during HC1 addition to 90°C and a solid dispersion of p-aminostyrene hydrochloride was formed. Time to reach saturation was about 20 minutes, however gas addition was continued for 1 hour. Temperature was maintained at 90°C using a regulated oil bath. Step 2

Upon completion of step 1, the input gas was shifted from HC1 to phosgene. The reactive gas was passed into the reactor until conversion of aminostyrene hydrochloride to p-isocyanatostyrene was complete. This was evidenced by the disappearance of the insoluble p-aminostyrene hydrochloride salt, formation of a clear reaction medium and a balance between input and offgas flow rates. The time for clearing was about 1 hour. Addition of phosgene was continued for 2 hours. Step 3

When the reaction was complete, the product mixture was cooled to 70°C and purged with nitrogen for 60 minutes to remove dissolved unreacted gasses. 0.1 Grams of Vazo-64 (a,a'-azobis(isobutyronitrile)) initiator was then added and polymerization allowed to proceed overnight before isolation of the reactive polymer product. Step

The polymer was precipitated in dry hexane, decanted, washed with additional hexane, decanted and then dissolving in dry THF. The resultant mixture was finally centrifuged to remove residual insoluble salts and impurities then transferred to nitrogen flushed serum bottles for storage. Analytical data is given in Table I-C-l.

i-ahi- τ-π-ι

Reagents, Reaction Parameters and Analysis Data for

Styrene-Isocyanatostyrene Polymers

Sample ♦ Composition (S-ICS) (Theory) Styrene (g) [moles]

P-Aminostyrene (g) [moles]

Toluene (ml) M (average) Elemental Anal. (T/A)

Carbon

Hydrogen

Nitrogen Composition (S-ICS)

(Actual by C,H,N)

Procedure D: Preparation of Homopolymers and Copolymers of Isocyanatoethyl Methacrylate with Methyl Methacrylate Into a set of 30 ml vacuum dried serum bottles were placed 0.05 g Vazo-52 (a,a'-azobis (a,g-dimethyl- valeronitrile) ) initiator, the appropriate amount of freshly distilled sodium dried THF (tetrahydrofuran) and mixtures of freshly purified monomers as designated in Table I-D-l. The bottles were flushed with dry nitrogen, sealed and placed in an ultrasonic bath at 50°C for 48 hours. After removal from the bath the samples were stored in the sealed bottles until ready for use. Samples were removed by syringe under positive nitrogen pressure and introduced into solutions containing reactive NLO active dyes just before spin- coating onto conductive substrates as described in the Examples. Bottles were resealed under dry nitrogen to retain an anhydrous inert atmosphere. Isocyanatoethyl methacrylate was purified by distillation. Methyl methacrylate was purified by passing through basic alumina.

Table l-P-l

Weight Volume THF Mw

Monomer mR JβL ■ml . moles mϋ ________

Dl MMA 9 2.559 2.711 0. 0256 27 23, 000 ICEM 1 0.440 0.4262 0.0028 D2 MMA 4 2.162 2.290 0. 0216 27 25, 300 ICEM 1 0.837 0.810 0.0054 D3 MMA 2 1.690 1.790 0.0169 27 25, 300 ICEM 1 1.309 1.266 0. 0084 D4 MMA 1 1.176 1.246 0.0118 27 18, 900 ICEM 1 1.823 1.763 0. 0118

D5 ICEM 1 3.0 2.901 0. 0193 27 4, 900

Experiment 2 NLO Active Dyes

Preparation of NLO Dye a:

This compound was prepared according to literature Peters, A. T., and Wild, M. S., J. Soc. Dyers Colour, Vol. 93, P 126, (1977) .

Preparation of NLO Dye hi

Disperse Red-1 was commerically available from Aldrich Chemical Company, Inc. (Stock # 21574-0) .

Prepara-.pn of NLQ Dye c: This compound was prepared according to Clement,

R.A., Tarn, W. and Wang, Y., US Patent: 4966730 (Oct. 30, 1990) . Preparation of (CH3C(0)) (CH3)N-biphenyl-S02C3F7 :

To 0.506 g (2.22 m oles) of 4-bromophenyl- N(CH3C(0)) (CH3) in 2 ml of dioxane was added 50 mg of Pd(PPl_3)4 in 2 ml of dioxane. The mixture was stirred for 10 min and then 1.050 g (2.22 mmoles) of 4- trimethylstannylphenyl-S02C3F7 in 2 ml of dioxane was added. The mixture was refluxed for 3 days, solvent was removed and the residue chromatographed with 50% EtOAc/hexane on silica gel. Thus obtained was 0.797 g (1.74 mmoles, 78.5%) of the desired product as a light yellow solid. Elemental analysis calculated for C18H14F7O3SN: C: 47.27; H: 3.09; Found: C: 47.09; H: 3.26. ^-H NMR (CD2CI2) : 8.2 (m, 2H) , 7.95 (m, 2H), 7.77 (m, 2H), 7.4 (m, 2H) , 3.4 (s, 3H) , 1.95 (s, 3H) .

Preparation of H(CH3)N-biphenylSθ2C3F7 :

To 0.400 g (0.875 mmoles) of the product from above was added 3 ml of EtOH and 3 ml of concentrated HC1. The mixture was refluxed overnight. To the cooled mixture was added 5-10 ml of CH2CI2 and the mixture neutralized to pH around 7 with 2.0M NaOH solution. The aqueous layer was extracted with 3X20 ml of CH2CI2. The organic layer was dried over N 2S0 and the solvent removed to give 0.293 g (0.70 mmoles, 81%) of the desired product as a light yellow solid. Elemental analysis calculated for C16H12NO2F7S: C: 46.27; H:

2.91; Found: C: 45.98; H: 2.72. -H NMR (CD2CI2) :

8.05 (m, 2H), 7.9 (m, 2H) , 7.6 (m, 2H), 6.8 (m, 2H), 3.0

(s, 3H), 1.6 (broad s, IH) .

Preparation of (HOC(CH3) (H)CH2) (CH3) -biphenylSθ2C3F7 :

To 0.283 g (0.681 mmoles) of the product from above was added 4 ml of EtOH and 0.95 ml (13.6 mmoles) of propylene oxide. The mixture was heated at 80°C for 5 days. The product was filtered and washed with a little EtOH to give 0.196 g of the product as a yellow solid. Solvent was removed from the filtrate to give an additional 105 mg of product (total yield of 311 mg, 0.64 mmoles, 93%). -H NMR (CD2CI2) : 8.1 (m, 2H), 7.9 (m,2H), 7.6 (m,2H) , 6.9 (m, 2H) 4.2 (m,IH) , 3.4 (d, J=6Hz, 2H), 3.1 (s, 3H), 1.9 (d, J*=3.5 Hz,lH), 1.3 (d, J^*~6Hz, 3H) .

Preparation of NLO Dye e: To 0.52 g (1.09 mmoles) of 4-fluorophenyl-Sθ2C6Fi3 and 0.110 g (1.09 mmoles) of (S)-(+)-2-pyrrolidine- methanol in 4 ml of DMSO was added 0.159 (1.15 mmoles) of K2CO3. The mixture was heated at 50°C for 4 days. To this mixture was added about 25 ml of water. Solvent was decanted off the paste that had formed and the paste was dissolved in CH2CI2 and dried over Na2S04. The solvent was removed to give 0.385 (0.71 mmoles, 65%) of the desired product as a light yellow oil. -^H NMR (CD2CI2) : 7.8 (m, 2H) , 6.8 (m, 2H) , 4.1 (m,lH), 3.7 (dd, IH) , 3.65 (dd, IH) , 3.58 (m, IH) , 3.37 (m, IH), 2.1 (m, 4H), 1.78 (t, IH) . .

Preparation of NLO Dve f:

3-nitrophenyl isocyanate is commerically available from Aldrich Chemical Company, Inc. (Stock #26,941-7)

Preparation pf NLQ Dye q^;

This compound can be prepared by methods analogous to those reported in J. Bourson, et.al. Optics Comm., Vol 722, p.367-370 (1989) and J. Bourson and B. Valeur, J. Phys. Chem., Vol 93, p.3871-3876 (1989). Preparation of NLO Dye h:

Ethyl 4-isocyanatobenzoate was commerically available from Aldrich Chemical Company, Inc. (Stock #15,934-4) .

Preparation of NLO Dye i:

To 4.50 g (0.0248 mmoles) of 4-nitrophenylacetic acid in 10 ml of ethanol was added 4.80 g (0.0248 mmoles) of 4-(diethylamino)salicylaldehyde in 10 ml of EtOH. To this mixture was added 5 ml of piperidine in 5 ml of EtOH. The dark brown mixture was refluxed for two days. The solvent was removed by rotary evaporation at 35^CC and the residue was passed through silica gel with CH2CI₂. The solvent was removed and the residue was flash chromatographed on silica gel eluted with CH₂CI₂. Thus obtained was 2.049 g (6.55 mmoles, 26%) of the desired product. The material can be recrystallized from CH₂CI₂/hexane. Elemental analysis calculated for C₁₈H_{20 2}O₃: C: 69.21; H: 6.45; Found: C: 69.26; H: 6.21. ⁱH NMR (CD₂CI₂) : 8.14 (d, J=8.9Hz, 2H), 7.59 (d, J=8.9Hz, 2H), 7.51 (d, J=16.33Hz, IH) , 7.41 (d, J=8.8Hz, IH), 6.99 (d, J=16.33Hz, IH), 6.33 (dd, J=8 8, 2.5Hz, IH) , 6.06 (d, J=2.5 Hz, IH), 5.1 (s, IH), 3.36 (q, J=7.08Hz, 4H), 1.17 (t, J=7.08Hz, 6H) .

EXAMPLE 1

To 0.06 g (0.191 mmoles) of NLO dye B in 1.3 ml of THF was added 0.89 ml (0.573 mmoles of NCO) of a 10% solution of polymer C-l in THF. The resulting solution was spin coated onto a glass slide coated with indium tin oxide. The resultant film was heated in a vacuum oven at 50°C for 60 min, 120°C for 60 min and then 150°C for 60 min. Prior to poling the sample was heated at 150°C for an additional 8 hours.

The sample was placed in poling apparatus so that it could be poled while monitoring the second harmonic signal which was generated. An electric field was applied and an SHG signal equal to about 30% of the maximum observed during the course of the poling process was observed within 10 min. The sample was then heated to 105°C at a heating rate of approximately 3°C/min. At approximately 90°C the signal was observed to decrease with increasing temperature, falling to nearly the original room temperature value. The sample was maintained at 105°C for 40 min, during which time the signal level was observed to increase by a factor of two. The sample was then rapidly cooled to room temperature at which time the electric field was removed. When the field was removed the SHG signal decreased to 65% of it's starting value within 5 min. After two days the sample was depoled by heating it to 150°C for three hours. It was then repoled in the manner described above. When the field was applied, an SHG signal equal to about 30% of the maximum observed during the course of the poling process was observed within 10 min. This time, during the heating phase, there was no significant loss of signal before reaching 105°C. After the sample was cooled to room temperature and the field was removed, the SHG signal decreased to 70% of it's starting value within 5 min. To accelerate the relaxation process, after making initial measurements at room temperature, the sample was placed in a vacuum oven maintained at 80°C, and removed from the oven only when subsequent measurements of the SHG signal were made. During the next 12 days the SHG signal decreased to 20% of this value. During the next 34 days, no additional decrease was noted.

EXAMPLE 2

To 0.030 g (0.124 mmoles) of of NLO dye a in 0.15 ml of THF was added 0.19 ml (0.124 mmoles of NCO) of a 10% solution of polyisocyanatoethyl methacrylate in THF (polymer D-5) . The resulting solution was spin coated onto a glass slide coated with indium tin oxide. The resultant film was heated in a vacuum oven at 50°C for 60 min and then 120°C for 5 hr.

The sample was placed in the poling apparatus so that it could be poled while monitoring the second harmonic signal which was generated. An electric field was applied and an SHG signal equal to about 10% of the maximum observed during the course of the poling process was observed within 10 min. The sample was then heated to 100°C at a heating rate of approximately 4°C/min. At 100°C the SHG signal was observed to decrease, presumably because of ionic conductivity effects. The sample was rapidly cooled to room temperature during which time the signal was observed to return to approximately 50% of its maximum value. The electric field was removed at room temperature and the SHG signal was observed to remain essentially constant during the next 27 days that the SHG was monitored.

EXAMPLE 3

To 0.020 g (0.042 mmoles) of NLO dye _l in 0.2 ml of THF was added 0.065ml (0.042 mmoles of NCO) of a 10% solution of polyisocyanatoethyl methacrylate in THF (polymer D-5) . The resulting solution was spin coated onto a glass slide coated with indium tin oxide. The resultant film was vacuum dried at room temperature overnight.

The sample was placed in the poling apparatus so that it could be poled while monitoring the second harmonic signal which was generated. An electric field was applied and an SHG signal equal to about 50% of the maximum observed during the course of the poling process was observed within 10 min. The sample was then heated to 50°C at a heating rate of approximately 1.8°C/min. During this heating cycle the SHG signal was observed to begin decreasing. The film was maintained at 50°C for approximately 15 min during-which time the SHG signal was observed to increase presumably because of a decrease in the ionic conductivity as the sample cured. The film was then heated successively to 55°C and 75°C during which time a similar sequence of events occurred. After maintaining the sample at 75°C for 45 min the film was rapidly cooled to room temperature during which time the SHG signal reached its maximum, value. When the field was removed the SHG signal decreased to 10% of it starting value within 5 min.

EXAMPLE 4

To 0.030 g (0.055 mmoles) of NLO dye ≤. in 0.2 ml of THF was added 0.15 ml (0.062 mmoles of NCO) of a 10% solution of the copolymer of isocyanatoethyl methacrylate and methyl methacrylate (1:1 ratio) in THF (polymer D-4) . The resulting solution was spin coated onto a glass slide coated with indium tin oxide. The resultant film was vacuum dried at room temperature overnight. The mixture from above was also spin coated onto a KBr disc and the reaction was followed by IR (-NCO band at 2280 cm"¹) . The intensity of the -NCO band decreased by 49% after heating at 170°C for 15 min. The sample was placed in the poling apparatus so that it could be poled while monitoring the second harmonic signal which was generated. An electric field was applied and an SHG signal equal to about 100% of the maximum observed during the course of the poling process was observed within 10 min. The sample was then heated to 180°C at a heating rate of approximately 1.5°C/min. As the sample was being heated the SHG signal was observed to decrease during heating and to increase during short,10 min, pauses at 50, 70, 80, 90, and 160°C. Above 90°C the signal decreased more during the heating cycles than it increased during the pauses. After maintaining the sample at 160°C for 20 min, the film was rapidly cooled to room temperature. When the field was removed the SHG signal decreased at rate of 0.5%/day over the next 60 days.

EXAMPLE 5

To 0.025 g (0.080 mmoles) of NLO dye b in 0.05 ml of THF was added 0.35 ml (0.099 mmoles of NCO) of a 10% solution of the copolymer of styrene-isocyanatostyrene (2:1 ratio) in THF (polymer C-3) . The resulting solution was spin coated onto a glass slide coated with indium tin oxide. The resultant film was vacuum dried at 50°C overnight and then at 120°C for 30 min and 150°C for 30 min. The mixture from above was also spin coated onto a KBr disc and the reaction was followed by IR. The intensity of the isocyanate at 2260 cm"¹ decreased by 96% after heating the film at 150°C for 15 min.

The sample was placed in the poling apparatus so that it could be poled while monitoring the second harmonic signal which was generated. An electric field was applied and an SHG signal equal to about 15% of the maximum observed during the course of the poling process was observed within 10 min. The sample was then heated to 100°C at a heating rate of approximately 4°C/min.

The sample was maintained at 100°C for approximately one hour. The sample was then rapidly cooled to room temperature. The electric field was removed and the SHG signal was observed to decrease to approximately 60% of its previous value during the first 10 min. During the next 20 days the SHG signal decreased at a rate of 4.3%/day.

EXAMPLE 6

To 0.040 g (0.127 mmoles) of NLO dye b in 0.2 ml of THF was added 0.30ml (0.159 mmoles of NCO) of a 13.37% solution of the copolymer of styrene-isocyanatostyrene (1:1 ratio) in THF (polymer C-2) . The resulting solution was spin coated onto a glass slide coated with indium tin oxide. The resultant film was vacuum dried at 50°C overnight and then at 120°C for 30 min and 150°C for 30 min. The mixture was also spin coated onto a KBr disc and the reaction followed by IR. The intensity of the -NCO band at 2275 cm"¹ decreased by 89% after heating at 120°C for 15 min.

The sample was placed in the poling apparatus so that it could be poled while monitoring the second harmonic signal which was generated. An electric field was applied and an SHG signal equal to about 13% of the maximum observed during the course of the poling process was observed within 10 min. The sample was then heated to 100°C at a heating rate of approximately 5°C/min. The sample was maintained at 100°C for approximately 15 min. It was then heated to 115°C for 10 min. The sample was then rapidly cooled to room temperature. The electric field was removed and the SHG signal was observed to decrease to approximately 70% of its previous value during the first 5 min. During the next 20 days the SHG signal decreased at a rate of 3.1%/day.

EXAMPLE 7

To 0.020 g (0.067 mmoles) of NLO dye £ in 0.25 ml of THF was added 0.17 ml (0.111 mmoles of NCO) of a 10% solution of polyisocyanatoethyl methacrylate in THF (polymer D-5) . The resulting solution was spin coated onto a glass slide coated with indium tin oxide. The resultant film was vacuum dried at room temperature overnight. The mixture from above was also spin coated onto a KBr disc and the reaction was followed by IR. The intensity of the -NCO band at 2280 cm"¹ decreased by 45% after heating at 170°C for 1 hr. This indicates that 75% of the dye has reacted with the polymer. The sample was placed in the poling apparatus so that it could be poled while monitoring the second harmonic signal which was generated. An electric field was applied and an SHG signal equal to about 11% of the maximum observed during the course of the poling process was observed within 10 min. The sample was then heated to 80°C at an heating rate of approximately 9°C/min. It was then heated to 100°C at an average rate of 1.0°C/min. The sample was then rapidly cooled to room temperature. The electric field was removed and the SHG signal was observed to decrease to approximately 55% of its previous value during the first 5 min. During the next 22 days the SHG signal decreased at a rate of 3.6%/day.

EXAMPLE 8

^oai-Q- _l OCHjCHj + OH

To 0.030 g (0.157 mmoles) of NLO dye h in 0.3 ml of THF was added 0.019 g (0.157 mmoles of OH) of a poly(p-vinyl phenol) (obtained from Polysciences with molecular weight between 9,000-11,000). The resulting solution was spin coated onto a glass slide coated with indium tin oxide. The resultant film was vacuum dried at room temperature overnight. The sample was placed in the poling apparatus so that it could be poled while monitoring the second harmonic signal which was generated. An electric field was applied and an SHG signal equal to about 65% of the maximum observed during the course of the poling process was observed within 10 min. The sample was then heated to 80°C at a heating rate of approximately 1.3°C/min. The film was maintained at 80°C for approximately 20 min during which time the SHG signal was observed to decrease to a value approximately 25% of the maximum. The film was rapidly cooled to room temperature. When the field was removed the SHG signal decreased to 50% of it starting value within 5 min. EXAMPLE 9

To 0.030 g (0.183 mmoles) of 3-nitrophenyl isocyanate (NLO dye f) in 0.35 ml of THF was added 0.022 g (0.183 mmoles of OH) of a poly(p-vinyl phenol) (obtained from Polysciences with molecular weight between 9,000-11,000). The resulting solution was spin coated onto a glass slide coated with indium tin oxide. The resultant film was vacuum dried at room temperature overnight.

The sample was placed in the poling apparatus so that it could be poled while monitoring the second harmonic signal which was generated. An electric field was applied and an SHG signal equal to about 100% of the maximum observed during the course of the poling process was observed within 10 min. The sample was then heated to 100°C at an heating rate of approximately 1.9°C/min. It was maintained at 100°C for 20 min and then rapidly cooled to room temperature. The electric field was removed and the SHG signal was observed to decrease to approximately 55% of its previous value during the first 5 min. During the next 22 days the SHG signal decreased at a rate of 1.6%/day.

EXAMPLE 10

To 0.015 g (0.043 mmoles) of NLO dye a in 0.3 ml of THF was added 0.22 ml (0.144 mmoles of NCO) of a 10% solution of polyisocyanatoethyl methacrylate in THF (polymer D-5) . The resulting solution was spin coated onto a glass slide coated with indium tin oxide. The resultant film was vacuum dried at 50°C for 60 min and then at 120°C for 30 min and then 150°C for 60 min.

The sample was placed in the poling apparatus so that it could be poled while monitoring the second harmonic signal which was generated. An electric field was applied and the sample was heated to 100°C. It was maintained at 180°C for approximately one hour during which time the SHG steadily increased to the maximum value observed during the experiment. The sample was then rapidly cooled to room temperature. The electric field was removed and the SHG signal was observed to decrease to approximately 20% of its previous value during the first 15 min. During the next 44 days the SHG signal decreased at a rate of 1.8%/day.

EXAMPLE 11

To 0.040 g (0.129 mmoles) of NLO dye ± was added to 0.02 ml (0.129 mmoles of NCO) of a 10% solution of polyisocyanatoethyl methacrylate in THF (polymer 5-C) . The resulting solution was spin coated onto a glass slide coated with indium tin oxide. The resultant film was vacuum dried at 50°C overnight, 120°C for 1 hour and then 150°C for 1 hour.

The sample was placed in the poling apparatus so that it could be poled while monitoring the second harmonic signal which was generated. An electric field was applied and an SHG signal equal to about 12% of the maximum observed during the course of the poling process was observed within 10 min. The sample was heated to 100°C at a heating rate of approximately 4.3°C/min. The sample was maintained at 100°C for approximately one hour. The sample was then rapidly cooled to room temperature. The electric field was removed and the SHG signal was observed to decrease to approximately 70% of its previous value during the first 10 min. To accelerate the relaxation process, after making initial measurements at room temperature, the sample was placed in a vacuum oven maintained at 80°C, and removed from the oven only when subsequent measurements of the SHG signal were made. During the next 59 days the SHG signal decreased at a rate of 0.7%/day. EXAMPLE 12

To 0.040 g (0.193 mmoles) of l-(4-nitrophenyl)- piperazine (dye j) in 0.25 ml of THF was added 0.12 ml (0.193 mmoles of NCO) of a 20% solution of polyglycidyl methacrylate in THF. The resulting solution was spin coated onto a glass slide coated with indium tin oxide. The resultant film was vacuum dried at 50°C for 2 hr and then 120°C for 6 hr and then 150°C for 15 hr.

The sample was placed in the poling apparatus so that it could be poled while monitoring the second harmonic signal which was generated. An electric field was applied and an SHG signal equal to about 5% of the maximum observed during the course of the poling process was observed within 10 min. The sample was then heated to 130°C at an heating rate of approximately 4°C/min. The SHG signal was observed to increase steadily until in reached its maximum value shortly after the temperature reached 130°C. The sample was maintained at 130°C for approximately 40 min. The sample was then rapidly cooled to room temperature. The electric field was removed and the SHG signal was observed to decrease to approximately 95% of its previous value during the first 5 min. To accelerate the relaxation process, after making initial measurements at room temperature, the sample was placed in a vacuum oven maintained at 80°C, and removed from the oven only when subsequent measurements of the SHG signal were made. During the next 23 days the SHG signal decreased at a rate of 2.3%/day. EXAMPLE 13

To 0.027 g (0.086 mmoles) of NLO dye b and 0.001 g (0.107 mmole) of 1,3-butanediol in 0.3 ml of THF was added 0.24 ml (0.086 mmoles of NCO) of a 6.5% solution of polymer D-5 in THF. The resulting solution was spin coated onto a glass slide coated with indium tin oxide. The resultant film was vacuum dried at 80°C for 30 min, 50°C for 60 min, 120°C for 60 min and then 150°C for 60 min.

The sample was placed in the poling apparatus so that it could be poled while monitoring the second harmonic signal which was generated. An electric field was applied and an SHG signal equal to about 20% of the maximum observed during the course of the poling process was observed within 10 min. The sample was then heated to 150°C at an heating rate of approximately 4°C/min. At approximately 120°C the SHG signal began decreasing, falling to near zero at 150°C. The sample was held at 150°C for 45 min. During this time the signal increased to approximately the value it had before the sample was heated. The sample was then rapidly cooled to room temperature. As the sample was cooled the SHG signal increased to the maximum value observed during the experiment. The electric field was removed and the SHG signal was observed to decrease to approximately 65% of its previous value during the first 5 min and an additional 30% during the next day. To accelerate the relaxation process, after making initial measurements at room temperature, the sample was placed in a vacuum oven maintained at 80°C, and removed from the oven only when subsequent measurements of the SHG signal were made. During the next 14 days the SHG signal decreased at a rate of 0.8%/day.

EXAMPLE 14

To 0.031 g (0.123 rnmoles) of disperse red 1 (dye b) and 0.001 g (0.123 mmole) of 1,4-butanediol in 0.3 ml of THF was added 0.28 ml (0.123 mmoles of NCO) of a 6.5% solution of polymer C-l in THF. The resulting solution was spin coated onto a glass slide coated with indium tin oxide. The resultant film was vacuum dried at 50°C for 60 min, 120°C for 60 min and then 150°C for 60 min.

The sample was placed in the poling apparatus so that it could be poled while monitoring the second harmonic signal which was generated. An electric field was applied and an SHG signal equal to about 15% of the maximum observed during the course of the poling process was observed within 10 min. The sample was then heated to 150°C at an heating rate of approximately 4°C/min. At approximately 130°C the SHG signal began decreasing, falling to near zero at 150°C. The sample was held at 150°C for 45 min. During this time the signal increased to approximately 45% of the maximum observed during the course of the poling process. The sample was then rapidly cooled to room temperature. As the sample was cooled the SHG signal increased to the maximum value observed during the experiment. The electric field was removed and the SHG signal was observed to decrease to approximately 65% of its previous value during the first 5 min and ^*»n 'c-i. n l 60% during the next day. To accelerate the relaxation process, after making initial measurements at room temperature, the sample was placed in a vacuum oven maintained at 80°C, and removed from the oven only when subsequent measurements of the SHG signal .were made. During the next 13 days the SHG signal was essentially unchanged.

EXAMPLE 15

To 0.028 g (0.089 mmoles) of disperse red 1 (dye b) and 0.0008 g (0.11 mmole) of 1,3-propane in 0.3 ml of THF was added 0.25 ml (0.111 mmoles of NCO) of a 6.5% solution of polymer D-5 in THF. The resulting solution was spin coated onto a glass slide coated with indium tin oxide. The resultant film was vacuum dried at 50°C for 60 min, 120°C for 60 min and then 150°C for 60 min.

The sample was placed in the poling apparatus so that it could be poled while monitoring the second harmonic signal which was generated. An electric field was applied and an SHG signal equal to about 15% of the maximum observed during the course of the poling process was observed within 10 min. The sample was then heated to 150°C at an heating rate of approximately 4°C/min. The sample was held at 150°C for 45 min. During this time the signal increased to approximately 55% of the maximum observed during the course of the poling process. The sample was then rapidly cooled to room temperature. As the sample was cooled the SHG signal increased to the maximum value observed during the experimen The electric field was removed and the SHG signal was observed to decrease to approximately 70% of its previous value during the first 5 min. To accelerate the relaxation process, after making initial measurements at room temperature, the sample was placed in a vacuum oven maintained at 80°C, and removed from the oven only when subsequent measurements of the SHG signal were made. During the next 13 days the SHG signal decreased at a rate of 2.0%/day.

Although preferred embodiments of the invention have been described hereinabove, it is to be understood that there is no intention to limit the invention to the precise constructions herein disclosed, and it is to be further understood that the right is reserved to all changes coming within the scope of the invention as defined by the appended claims.

Claims

CLAIMS What is claimed is:

1. A process for the production of a shaped part, comprising:

(a) reacting

(i) a polyfunctional polymer containing active groups; with

(ii) a compound containing a polar dye moiety and one reactive group; said reacting forming a polymer having side chains containing one or more polar dye moieties; and

(b) shaping the part; wherein said shaping is carried out before or substantially simultaneously with said reacting such that when substantial reacting occurs the mixture of said polyfunctional polymer and said compound is substantially in the final shape of the shaped part.

2. The process as recited in Claim 1 comprising the additional step of aligning said dye moieties in conformance with an externally applied electric field.

3. The process as recited in Claim 2 wherein said aligning takes place simultaneously with said reaction.

4. The process as recited in Claim 2 wherein said aligning takes place about at or above the glass transition temperature of said polymer.

5. The process as recited in Claim 2 wherein said active or said reactive groups are selected from the group consisting of epoxy, aziridinyl, isocyanate, acyl halide, carboxyl anhydride, and alkoxysilyl.

6. The process as recited in Claim 5 wherein said active or reactive groups are selected from the group consisting of epoxy and isocyanate.

7. The process as recited in Claim 6 wherein said active or said reactive group is isocyanate.

8. The process as recited in Claim 2 wherein said polyfunctional polymer has a degree of polymerization of about 10 to about 3,000.

9. The process as recited in Claim 8 wherein said polyfunctional polymer has a degree of polymerization of about 50 to about 1,000.

10. The process as recited in Claim 2 wherein the polyfunctional polymer is made from acrylic or styrenic monomers.

11. The process as recited in Claim 10 wherein said monomers are selected from the group consisting of acryloyl chloride, maleic anhydride, methacryloyl chloride, 2-isocyanatoethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, 4-isocyanatostyrene, 3- (2-isocyanato-2-propyl)-α-methylstyrene, 2-hydroxyethyl methacrylate, 4-aminostyrene, methacrylic acid, 3- trimethoxysilylpropyl methacrylate, methyl methacrylate, styrene, 4-methylstyrene, cyclohexyl methacrylate, ethyl acrylate, and phenyl methacrylate.

12. The process as recited in Claim 11 wherein said monomers are selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, 2-isocyanato- ethyl methacrylate, 4-isocyanatostyrene, styrene, and methyl methacrylate.

13. The process as recited in Claim 2 wherein said compound is selected from the group consisting of 4-(N- 2-hydroxyethyl-N-ethylamino)-1-(2,2-dicyanoethenyl)- benzene, 4-(N-2-hydroxyethyl-N-ethylamino)-4'- nitroazobenzene, 4-(2-hydroxyethoxy)- '-nitrostilbene, 4-{4'-[N-(2-methyl-3-hydroxypropy1)-N-methyl]- biphenylyl} (heptafluoropropyl)sulfone, [4—(2— hydroxymethyl-l-pyrrolidinyl)phenyl] (tridecafluoro- hexyl)sulfone, 3-nitrophenylisocyanate, ethyl 4- isocyanatobenzoate, and 4-dicyanomethylene-2-methyl-6- [4-(N-2-hydroxyethyl-N-ethylamino)-α-styryl]-4H-pyran.

14. The process as recited in Claim 12 wherein said compound is selected from the group consisting of

4-(N-2-hydroxyethyl-N-ethylamino)-1-(2,2-dicyano- ethenyl)benzene, 4-(N-2-hydroxyethyl-N-ethylamino)-4'- nitroazobenzene, 4-(2-hydroxyethoxy)-4'-nitrostilbene, 4-{4'-[N-(2-methyl-3-hydroxypropyl)-N-methyl]- biphenylyl} (heptafluoropropyl)sulfone, [4-(2- hydroxymethyl-l-pyrrolidinyl)phenyl] (tridecafluoro- hexyl)sulfone, 3-nitrophenylisocyanate, ethyl 4- isocyanatobenzoate, and 4-dicyanomethylene-2-methyl-6- [4-(N-2-hydroxyethyl-N-ethylamino)-α-styryl]-4H-pyran.

15. The process as recited in Claim 14 wherein said polyfunctional polymer has a degree of polymerization of about 10 to about 3,000.

16. The process as recited in Claim 2 wherein the polyfunctional polymer has at least about one active group for each two monomeric units.

17. The process as recited in Claim 16 wherein the polyfunctional polymer has at least about one active group for each three monomeric units.

18. The process as recited in Claim 15 wherein the polyfunctional polymer has at least about one active group for each two monomeric units.

19. The process as recited in Claim 18 wherein the polyfunctional polymer has at least about one active group for each three monomeric units.

20. The process as recited in Claim 1 wherein said polyfunctional polymer is crosslinked simultaneous with said reaction.

21. The process as recited in Claim 2 wherein said polyfunctional polymer is crosslinked simultaneous with said reaction.

22. The process as recited in Claim 3 wherein said polyfunctional polymer is crosslinked simultaneous with said reaction.

23. The process as recited in Claim 6 wherein said polyfunctional polymer is crosslinked simultaneous with said reaction.

24. The process as recited in Claim 8 wherein said polyfunctional polymer is crosslinked simultaneous with said reaction.

25. The process as recited in Claim 17 wherein said polyfunctional polymer is crosslinked simultaneous with said reaction.

26. The process as recited in Claim 20 wherein crosslinks formed by reaction of isocyanate active groups with a diol containing 8 or less carbon atoms.

27. The process as recited in Claim 26 wherein said diol is ethylene diol, 1,3-propanediol, 1,3- butanediol, or 1,4-butanediol.