RU2464285C1 - Electrooptic polymerisable acrylic composition, electrooptic cross-linked polymer material and method for production thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: electrooptic polymer material is obtained from a polymerisable acrylic composition which consists of an acrylic monomer containing an electron-donor group, an acrylic monomer containing an electron-acceptor group, a bifunctional acrylic oligomer, a polymerisable monomer-solvent and a radical photochemical or thermal polymerisation initiator, with the following ratio of components in wt %: acrylic monomer containing an electron-donor group 1-15, acrylic monomer containing an electron-acceptor group 1-15, bifunctional acrylic oligomer 5-55, polymerisable monomer-solvent 0-65, initiator 0.1-5.0. A method of producing an electrooptic cross-linked polymer material is also disclosed, which involves a step for preparing an acrylic composition and solidification thereof.

EFFECT: fixed arrangement of electrophorus donor and acceptor groups in electrooptic cross-linked polymer material, optimum alignment of donor-acceptor dipoles and the required physical parameters: elasticity, mechanical strength and impact strength.

6 cl, 1 tbl, 41 ex

Description

The invention relates to electro-optical polymeric materials that change the refractive index when an electric field is applied. More specifically, the invention relates to crosslinked electro-optical polymer materials obtained by three-dimensional polymerization of an electro-optical polymerization-capable acrylic composition and a method for carrying out this process. Electro-optical polymeric materials are intended for the manufacture of non-linear optical devices, in particular terabit modulators of optical signals for high-speed transmission of information in fiber-optic communication lines (FOCL) and optical processors.

The development of high-speed FOCLs and optical processors requires the creation of optical signal modulators with switching times of the order of several picoseconds, which will allow transmitting optical information at a terabit speed. Existing modulators, in particular based on lithium niobate, have switching times of the order of hundreds of picoseconds, which does not allow reaching terabit speeds.

Currently, the main way to create high-speed modulators and light switches involves the use of the electro-optical effect in polymeric materials. New materials are being developed with a large electro-optical effect and picosecond switching times. These works are carried out by leading companies in this field: British Telecom (England), France Telecom and Alcatel (France), Nortel (Canada), Allied Signal Inc., Coming Inc., Zenastra and Telephotonics (USA), NTT (Japan), etc. Special electro-optical chromophores were synthesized with the magnitude of the electro-optical coefficient and the modulation speed of the optical signal, an order of magnitude greater than that of modulators based on lithium niobate.

The main approach to creating materials for the implementation of second-order nonlinear optical effects involves the implementation of a “push pool” mechanism: a donor-π-acceptor system (D-π-A) (US Patent Nos. 6,067,186, 6,090,332), which involves the transfer of charge from a donor to the acceptor through a system of conjugated bonds. In such molecular structures, significant values of the second-order nonlinear optical effect are achieved, since the first molecular electronic hyperpolarizability (β or μβ), which is a measure of this effect, can vary significantly due to a change in the structure of D-π-A elements. The most famous systems using thienyl derivatives as A (US Application 2003/0183812, 2006/0114552).

Another direction for the creation of modulators provides for the interaction of DA through their fixation in a polymer matrix. Known works use electrochromic structures built into the polymer chain: the components of the electrochromic are introduced into an inert polymer, for example, 2,3-bis - [(3-thienyl) oxy] propyl ether of 3-thiophenecarboxylic acid with thiophene and pyrrole into the polymethyl methacrylate matrix (Europ Polymer J. 2004. V.40. P.2442) or 3- (1,1-dicyanoethyl) -1-phenyl-1H-pyrazole in a polyetherketone matrix (JOSA B. 2002. V.19. P.215). It is also possible to introduce an electrochromic group into the side chain of a linear polymer, for example, poly-N-vinylcarbazole doped with acceptor compounds: 1-butoxyl-2,5-dimethyl-4- (4-nitrophenylazo) benzene and 2,4,7-trinitro 9-fluorenone (JOSA B. 1999. V.16. P.215).

Further development of this direction led to the creation of materials obtained by copolymerization of monomers containing donor and acceptor molecules in the side chain.

The closest analogue (prototype) of the present invention (Polymer. 2001. V.42. P.1101-1107) provides for copolymerization of acrylic monomers to obtain an electro-optical material, one of which contains a donor group of a carbazole derivative, and the other an acceptor group of a nitroazobenzene derivative. The work describes the synthesis of donor and acceptor monomers and the process of their thermal copolymerization in toluene at 60 ° C for 48 hours in a vacuum sealed ampoule in the presence of 0.5% azo-bis-isobutyronitrile as an initiator.

The main disadvantage of the solution presented in the prototype is that two acrylic monomers containing bulky side substituents are copolymerized, and for steric reasons, donor and acceptor groups are located on opposite planes relative to the polymer chain, which virtually eliminates electronic interactions between them. Meanwhile, it is these interactions that determine the electro-optical properties of the material. In addition, it is shown (US Patent No. 5100971) that structurally similar poly (meth) acrylates containing a carbazole substituent are hard brittle materials with very low adhesion to commonly used substrates.

A significant drawback of the solution proposed in the prototype is the impossibility of orientation of the dipoles and its fixing. To achieve a high electro-optical coefficient of the modulator, it is necessary to orient the donor-acceptor dipoles in an electric field and then fix the optimal orientation (US Patent No. 7391938). In all known solutions for the production of polymer electro-optical materials, linear high polymers with side electrophore groups having a rather high glass transition temperature are used. In such polymers, the orientation of dipoles is to some extent possible only at temperatures above the glass transition temperature, that is, under conditions where thermal decomposition of electrophore groups is possible.

The disadvantages of the solution chosen for the prototype, as well as the solutions in the other sources listed above, include the method of producing films of electro-optical material by pouring a solution of a linear polymer in an inert solvent. This approach does not allow one of the most promising technologies for creating FOCLs and optical processors to be implemented, which provides for the formation of a planar waveguide system using laser stereolithography or photoreplication. This technology has been successfully used to produce conventional waveguides through the use of photopolymerizable compositions that cure in specified areas when exposed to a laser beam or non-monochromatic light through a template (US Patent No. 6917749).

The objective of the invention is the creation of a polymerization-capable composition capable of three-dimensional radical copolymerization during photochemical or thermal initiation with the formation of electro-optical crosslinked cross-linked polymer material with a fixed arrangement of donor and acceptor groups and which allows the orientation of the donor-acceptor dipoles and the polymerization process under the conditions of an applied electric field maintain optimal orientation in electro-optical material. The composition should possess the necessary physical parameters: viscosity, thixotropy, transparency in the telecommunication spectral regions.

The objective of the invention is the creation of an electro-optical cross-linked polymer material obtained by three-dimensional radical polymerization of a polymerization-capable composition during photochemical or thermal initiation, which due to the cross-linked network structure will differ in the fixed arrangement of electrophore donor and acceptor groups with the optimal orientation of the donor-acceptor dipoles and will have the necessary physical parameters : elasticity, mechanical strength, Darnay strength and other properties necessary for the electro-optical material.

The objective of the invention is also the development of a method for producing an electro-optical crosslinked cross-linked polymer material with a fixed arrangement of donor and acceptor groups by three-dimensional radical copolymerization of a liquid acrylic composition during photochemical or thermal initiation.

The solution to this problem is achieved:

- the proposed electro-optical polymerization-capable acrylic composition consisting of an acrylic monomer containing an electron-donating moiety, an acrylic monomer containing an electron-withdrawing moiety, a bifunctional acrylic oligomer, a polymerization-based solvent monomer and an initiator of radical photochemical or thermal polymerization, with the following ratio:% wt.

Acrylic monomer containing electron donor group 1-15, Acrylic monomer containing electron withdrawing group 1-15, Bifunctional Acrylic Oligomer 5-55, Polymerization Solvent Monomer 0-65 Polymerization initiator 0.1-5.0.

The proposed electro-optical acrylic composition as an acrylic monomer containing an electron-donating moiety may contain ω- (N-carbosolyl) alkyl acrylates.

The proposed electro-optical acrylic composition as an acrylic monomer containing an electron withdrawing moiety may contain 4- (ω-acryloyloxyalkyl) -4'-nitroazobenzenes.

The proposed electro-optical acrylic composition as a bifunctional acrylic oligomer may contain either oligoester (meth) acrylates, or epoxy acrylates, or oligocarbonate methacrylates, or oligourethane (meth) acrylates, or fluorinated bifunctional acrylic oligomers;

- the proposed electro-optical crosslinked polymeric material that changes the refractive index when applying an electric field, obtained by three-dimensional radical polymerization of the inventive polymerization-capable monomer-oligomeric acrylic composition during photochemical or thermal initiation;

- the proposed method for producing the inventive electro-optical crosslinked cross-linked polymer material, comprising the step of preparing the inventive polymerization-capable acrylic composition and the stage of curing it, consisting of the following operations:

1. dissolving an acrylic monomer containing an electron withdrawing moiety in a polymerization solvent monomer;

2. adding to the resulting solution an acrylic monomer containing an electron-donating moiety;

3. heating the resulting mixture at 40-50 ° C for 5-10 minutes;

4. adding to the resulting solution a bifunctional acrylic oligomer and a polymerization initiator and mixing until complete dissolution to obtain a composition;

5. curing the obtained composition by photochemical or thermal initiation of three-dimensional radical polymerization with the formation of electro-optical cross-linked network polymer material.

Proposed in the present invention, the approach to the production of electro-optical materials allows us to solve the basic structural and technological problems of creating elements of fiber optic links and electro-optical modulators, which cannot be implemented using the solution given in the prototype. In particular, copolymerization of donor and acceptor monomers in the presence of a bifunctional oligomer makes it possible to obtain a network polymer with a fixed arrangement of donor and acceptor groups. It becomes possible to control the size of the mesh polymer cells by selecting the length of the oligomeric block (the group between the two terminal acrylic groups in the bifunctional oligomer) and / or the interstitial distance (due to copolymerization with the monomer) to ensure free placement and orientation of the electrochromic groups.

Moreover, since the initial composition is a viscous liquid, the orientation of the dipoles under the conditions of an applied electric field is carried out without difficulty, and the subsequent three-dimensional polymerization fixes the optimal orientation of the donor-acceptor dipoles in the network electro-optical polymer.

The proposed polymerization-based acrylic composition is a typical oligomer-monomer composition and can be processed into products (films, waveguides, etc.) by methods conventional for oligomers without the use of inert solvents. For example, films of adjustable thickness can be obtained by the method of centrifugal technology (“spin coating”), and the use of photoinitiated polymerization allows you to get products of arbitrary shape by laser stereolithography or photoreplication.

The inventive electro-optical cross-linked polymer material can be used for the manufacture of non-linear optical devices, in particular for the manufacture of terabit modulators of optical signals for high-speed transmission of information in fiber-optic communication lines (FOCL) and optical processors.

DETAILED DESCRIPTION OF THE INVENTION

To solve the problem of manufacturing high-quality cross-linked electro-optical polymer material, the authors conducted an extensive study. As a result, the main factors were found that affect the possibility of obtaining a cross-linked polymer in the presence of highly polar donor and acceptor groups, on the one hand, determining the realization of the electro-optical effect by the “push-pool” mechanism, and on the other, exhibiting the properties of radical reaction inhibitors, including and polymerization.

The first factor that determines the possibility of obtaining a cross-linked electro-optical polymer is the choice of the chemical structure of acrylic compounds (oligomers and monomers). The structure should exclude possible specific reactions involving electrochromic groups, which can lead to a loss of electro-optical properties, especially during curing.

The second factor is the type of initiator and the initiation conditions for three-dimensional radical polymerization, which determines the initiation rate, concentration of free radicals, rate constants of the polymerization process and, which is especially important, determines the contribution of reactions of free radicals with electrochromic groups.

The third factor that determines the possibility of obtaining a high-quality cross-linked electro-optical polymer is related to the need to control the size of the mesh polymer cells by selecting the length of the oligomeric block (the group between the two terminal acrylic groups in the bifunctional oligomer) and / or the interstitial distance (due to copolymerization with the monomer) for ensuring free placement and orientation of electrochromic groups.

First, we consider the proposed acrylic composition, and then other objects of the claimed invention.

The proposed electro-optical polymerization acrylic composition consists of an acrylic monomer containing an electron donor moiety, an acrylic monomer containing an electron withdrawing moiety, a bifunctional acrylic oligomer, a polymerization solvent-monomer and a polymerization initiator.

As an acrylic monomer containing an electron-donating moiety, the composition includes acryl-substituted carbazole derivatives — acrylation products of N- (hydroxyalkyl) carbazoles. Preferred examples are 2- (N-carbosolyl) ethyl acrylate (AMD-1) (J. Polymer ScL, Part C, 1988, V.26, P.441; U.S. Patent 5100971) and 3- synthesized for the first time (2, 7-dichlorocarbazol-9-yl) propyl acrylate (AMD-2):

Compounds of this type are the most commonly used electron donors, but other polymerizable electron donor compounds can be used in the proposed composition.

As an acrylic monomer containing an electron withdrawing moiety, it is preferable to use acrylic substituted nitroazobenzene derivatives - polymerization analogs of the known electro-optical compound DR-1 (US Patent 6449417). In the experiments performed, the best results were obtained using 4- (2-acryloloxyethyl) -2,5-dimethyl-4'-nitroazobenzene (AKA-1) (Polymer. 2001. V.42. P.1101) and the first synthesized 4- ( 6-acryloyloxyhexyl) -3-methyl-4'-nitroazobenzene (AKA-2):

Compounds of this type are the most commonly used electron acceptors, but other polymerizable electron-withdrawing compounds can be used in the proposed composition.

The bifunctional acrylic oligomer acts as a crosslinking agent for acrylic monomers containing an electron-donating and electron-withdrawing moiety. Its structure, molecular weight and concentration determine the density of the spatial network, and the nature of the oligomeric block determines the orientation of the donor – acceptor in the dipole space. Any oligomer containing two (meth) acrylic groups can be used in this composition if it meets the following requirements:

- combination with electronically active acrylic monomers in a liquid composition, in the copolymerization process and in the final electro-optical crosslinked polymer material;

- low absorption in telecommunication spectral regions;

- achieving an acceptable magnitude of the electro-optical effect.

In the proposed composition can be used oligoester (meth) acrylates based on dihydric alcohols, glycols, bis-phenols, epoxy acrylates - products of (meth) acrylation of epoxy Diane oligomers, oligocarbonate methacrylates, oligourethane (meth) acrylates, obtained as the "isocyanate" method, and without the use of isocyanates, and di (meth) acrylates of other known classes.

The most promising from the point of view of use in the proposed composition are commercially available epoxy acrylates based on diphenylpropane and its ethoxylated and glycated derivatives, the structures of which are given below (DA-1, DA-2 and DA-3, respectively):

Another valuable bifunctional acrylic oligomer is the commercially available OKM-2 oligocarbonate methacrylate:

Of the oligourethane methacrylates, the most interesting is the oligomer based on isophorondiisocyanate (OUM):

From the point of view of transparency of cross-linked electro-optical material in the telecommunication spectral regions, fluorinated bifunctional oligomers of the general formula (FA-4 and FA-6) are of particular interest:

The polymerization-based solvent monomer is preferably used in the claimed composition, since the electronically active acrylic monomers AMD and AKA, as well as most of their analogues, are solid compounds poorly soluble in organic solvents. In some cases, it is possible to dissolve them directly in a bifunctional acrylic oligomer, but, as a rule, the latter are highly viscous compounds, which is why the dissolution process requires a period of time unacceptable from a technological point of view. The use of a low-viscosity polymerization-capable solvent monomer allows not only to sharply improve the process of obtaining the claimed composition, but also provides an additional opportunity to control the density of the mesh in a crosslinked electro-optical material.

In principle, any compound capable of radical polymerization and / or copolymerization can be used in this composition if it contains a group such as (meth) acryloyl, vinyl, allyl or styrene. From the point of view of the speed of the polymerization reaction, derivatives of acrylic acids are most preferred. Since the electron-active acrylic oligomers AMD and AKA are highly polar compounds, the most useful polymeric polymerization solvent monomers such as 2-phenoxyethyl methacrylate (FEM), N-vinylpyrrolidone (VP) and isobornyl acrylate (IBA) are most useful from the point of view of this invention.

The preparation of a crosslinked electro-optical material by three-dimensional radical polymerization of said acrylic composition is not significantly limited, any known method of initiating polymerization can be used. Peroxides and azo compounds for thermally initiated polymerization, photoinitiators for photopolymerization in the UV and visible spectral regions, high-energy radiation, as well as any combination of these effects can be used as initiators.

Typical thermal polymerization initiators include diacyl peroxides, for example benzoyl peroxide, peroxy esters, for example dauryl peroxide, percarbonates and azo compounds, for example 2,2'-azobisisobutyronitrile (ABN). Most preferred for the polymerization of the proposed composition is ABN.

In the polymerization under UV irradiation, benzoin derivatives, for example benzoin butyl ether, ketals, for example benzyl methyl ketal, hydroxy ketones, for example hydroxycyclohexyl phenyl ketone, are used as photoinitiator. Photoinitiators can also be used in combination of 2 or more components, as well as in a mixture with thermal curing initiators.

For photopolymerization of the claimed composition under UV irradiation, the most preferred initiator is a mixture of (1: 1) diphenyl (2,4,6-trimethylbenzoyl) phosphine and 2-hydroxy-2-methylpropiophenone (PI).

Most of the above developments for photochemical initiation used a 1000 W high-pressure mercury lamp.

The following examples are provided for the purpose of further disclosing the present invention.

Example 1. Synthesis of 3- (2,7-dichlorocarbazol-9-yl) propyl acrylate (AMD-2).

5.6 g (0.02 mol) of 3- (2,7-dichlorocarbazol-9-yl) propanol-1 and 50 ml of tetrahydrofuran (THF) were charged into a 4-necked flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel. ) and then 3.3 ml (2.4 g, 0.024 mol) of triethylamine in 10 ml of THF. The reaction mixture was cooled to 2 ° C and a solution of 2.0 g (0.022 mol) of acrylic acid chloride in 10 ml of THF was added dropwise, maintaining the temperature within 2-4 ° C. Then the reaction mixture was kept for 1 hour at room temperature and 3 hours at 40-42 ° C. After cooling, the reaction mixture was poured into 200 ml of a 2% hydrochloric acid solution at 0 ° C, and the separated product was washed on a Buchner funnel with water until the reaction to chlorine ions was negative. After drying in a vacuum oven, 5.8 g (87%) of a white product, 3- (2,7-dichlorocarbazol-9-yl) propyl acrylate, was obtained; 140-141 ° C after recrystallization from ethanol. The structure of this product, as well as the products of examples 2-5, is proved by elemental analysis, data of electronic and IR spectroscopy and liquid chromatography.

Example 2. Diazotization of p-nitroaniline.

34.5 g (0.25 mol) of p-nitroaniline was dissolved by heating in 500 ml of water containing 78 g of hydrochloric acid (36%) (0.75 mol). To a solution cooled to 0 ° C, 17.25 g (0.25 mol) of sodium nitrite was added with stirring. The reaction mixture was slowly heated to 34 ° C, kept at this temperature until a negative reaction to nitrite ions (control by iodine starch paper) and a diazo salt of p-nitroaniline was obtained.

Example 3. Synthesis of 4-hydroxy-3-methyl-4'-nitroazobenzene.

To a solution of 27 g (0.25 mol) of o-cresol and 10 g (0.25 mol) of NaOH cooled to 0 ° C, a solution of p-nitroaniline diazo salt was added dropwise with stirring. The dye precipitate was filtered off, washed with water until neutral and dried under vacuum at 40 ° C to constant weight. Received 52.7 g (82%) of the target product.

Example 4. Synthesis of 4- (6-hydroxyhexyl) -3-methyl-4'-nitroazobenzene.

25.7 g (0.1 mol) of 4-hydroxy-3-methyl-4'-nitroazobenzene, 25.4 g (0.105 mol) of 6-bromohexanol and 13.8 g (0.1 mol) of anhydrous potassium carbonate were heated in 300 ml of acetone for 48 hours. The reaction mixture was poured into 1.5 L of a 10% solution of NaOH in water. The precipitate was filtered off, washed until neutral, dried under vacuum at 40 ° C to constant weight. 24.8 g (62%) of 4- (6-hydroxyhexyl) -3-methyl-4'-nitroazobenzene are obtained.

Example 5. Synthesis of 4- (6-acryloyloxyhexyl) -3-methyl-4'-nitroazobenzene (AKA-2).

A solution of 10.53 g (0.03 mol) of 4- (6-hydroxyhexyl) -3-methyl-4'-nitroazobenzene and 3.6 g (0.036 mol) of triethylamine in 50 ml of THF was slowly added to a solution 2, 9 g (0.033 mol) of acrylic acid chloride in 3 ml of THF. Then the reaction mixture was heated at 30 ° C for 2 hours. The mixture was poured into 200 ml of a 10% hydrochloric acid solution with ice. The precipitate was washed and dried under vacuum at 30 ° to constant weight. Received 8.26 g (67%) of 4- (6-acryloyloxyhexyl) -3-methyl-4'-nitroazobenzene.

Example 6. Preparation of a polymerization-capable monomer-oligomeric acrylic composition for thermopolymerization.

0.0397 g (5.6%) AKA-2 was added to 0.2444 g (35.3%) FEM and heated at 40-45 ° С with constant stirring until completely dissolved. To the resulting solution, 0.0305 g (4.4%) of AMD-2 and 0.3785 g (54.7%) of OUM were successively added. After complete homogenization to a clear composition, yield 100%, 0.0116 g (1.65% of the total weight of the composition) ABN was added and stirred at room temperature until the initiator was completely dissolved.

Examples 7-14. Preparation of polymerization-capable monomer-oligomeric acrylic compositions for thermopolymerization.

By the methodology described in example 6, obtained compositions whose compositions are specified in table 1.

Example 15. Preparation of a polymerization-capable monomer-oligomeric acrylic composition for photopolymerization.

To the composition, the preparation of which is described in example 6, 3-4% (to the total weight of the composition) of PHI for photoinitiated polymerization was added and stirred at room temperature until the initiator was completely dissolved.

Examples 16-23. Preparation of polymerization-capable monomer-oligomeric acrylic compositions for photopolymerization.

By the methodology described in example 15, obtained compositions, the compositions of which are also specified in table 1.

Table 1 The compositions of the polymerization monomer-oligomeric acrylic compositions. Example No. Component composition, wt.% AMD-2 AKA-2 FEM IBA VP YES OKM OUM FA-4 For thermopolymerization, ABN, 1.65% 7 7.1 5.9 49.9 37.1 8 15.0 4.7 64.3 16,0 9 3,5 4.2 43.7 43.6 5,0 10 8.3 10,2 35,4 46.1 eleven 3.3 4.0 42.0 50.7 12 7.9 10.0 36,2 45.9 13 7.6 6.3 23.7 62,4 fourteen 1,0 12.7 23.7 62.6 For photopolymerization, FI, 3-4% fifteen 4.4 5,6 35.3 54.7 16 7.1 5.9 49.9 37.1 17 8.8 10.9 64.3 16,0 eighteen 6.7 1,0 43.7 48.6 19 3,5 15.0 35,4 46.1 twenty 3.3 4.0 42.0 50.7 21 7.9 10.0 36,2 45.9 22 7.6 6.3 23.7 62,4 23 7.5 6.2 23.7 62.6

Example 24. Obtaining a crosslinked electro-optical material. The composition of the composition shown in example 6 was applied to a casting mold formed by a silicate glass substrate and a 30-μm-thick single-sided tape film frame. The mold was covered with silicate glass coated with a release coating on the working surface and the assembly was heated at 80-82 ° C for 1 hour. Got a transparent strong film of bright red color.

Examples 25-32. Getting cross-linked electro-optical material.

According to the methodology described in example 24, samples of crosslinked electro-optical material in the form of transparent strong films of bright red color were obtained from the compositions of examples 7-14.

Example 33. Obtaining cross-linked electro-optical material.

The composition of the composition shown in example 15 was applied to a casting mold formed by a silicate glass substrate and a 30 μm thick single-sided tape frame. The mold was covered with quartz glass coated with a release coating on the working surface, and the assembly was irradiated with a 1000 W mercury lamp for 4-5 minutes. After disassembling the forms, a transparent, strong film of bright red color was obtained.

Examples 34-41. Getting cross-linked electro-optical material.

According to the methodology described in example 33, samples of crosslinked electro-optical material in the form of transparent strong films of bright red color were obtained from the compositions of examples 16-23.

All developed compositions shown in Table 1 have satisfactory physicochemical properties: their composition is selected so that their viscosity (200-3000 cP) allows the composition to spread over the substrate, including under the conditions of centrifugal technology ("spin-coating" ), the polymerization rate under UV irradiation (not more than 40 sec for a 500 μm film) is sufficient to implement the most advanced technologies for manufacturing optical products, after polymerization of the composition, a durable elastic material with acceptable adhesion to p zlichnym substrates, it is suitable for the manufacture of waveguides, switches and other electro-optic products in their properties.

The content of electro-optical monomers in the developed compositions covers the range of their concentrations given in the known patent and literature sources. The content of each of the electro-optical monomers and their ratio is determined by the conditions of the specific application and the required value of the electro-optical effect, but in all cases the complex physicochemical and deformation-strength properties of the developed composition and material will ensure the production of a high-quality product.

Thus, the present invention has developed a new approach to the creation of cross-linked electro-optical polymeric materials, providing for the copolymerization of acrylic monomers containing an electron-donating and electron-withdrawing substituent with mono- and difunctional acrylates during thermal or photoinitiation. In accordance with published data, the developed polymer material contains all the necessary structural elements for the realization of electro-optical properties, while the relative concentration and ratio of donor and acceptor groups in the material can vary widely. When polymerizing a liquid composition under the conditions of an applied electric field, it is possible to efficiently orient dipoles with their subsequent fixation in a mesh material, which, according to well-known theoretical developments, will make it possible to sharply reduce the switching voltage, increase the switching times to several picoseconds, and achieve an optical signal modulation depth close to 100% .

Claims (6)

1. Electro-optical polymerization acrylic composition consisting of an acrylic monomer containing an electron-donating moiety of an acrylic monomer containing an electron-withdrawing moiety, a bifunctional acrylic oligomer, a polymerization solvent-monomer and an initiator of radical photochemical or thermal polymerization in the following ratio of components, wt.
Acrylic monomer containing electron donating moiety 1-15 Acrylic monomer containing an electron withdrawing moiety 1-15, Bifunctional Acrylic Oligomer 5-55 Polymerization Solvent Monomer 0-65 Initiator 0.1-5.0 2. Electro-optical polymerization-acrylic composition according to claim 1, characterized in that, as an acrylic monomer containing an electron-donating moiety, it contains 2- (N-carbosolyl) ethyl acrylate or 3- (2,7-dichlorocarbazol-9-yl) propyl acrylate. 3. The electro-optical polymerization-capable acrylic composition according to claim 1, characterized in that, as an acrylic monomer containing an electron withdrawing moiety, it contains 4- (2-acryloyloxyethyl) -2,5-dimethyl-4'-nitroazobenzene or 4- (6- acryloyloxyhexyl) -3-methyl-4'-nitroazobenzene. 4. Electro-optical polymerization acrylic composition according to any one of claims 1 to 3, characterized in that it contains oligoester (meth) acrylates or epoxy acrylates or oligocarbonate methacrylates or oligourethane (meth) acrylates or fluorinated bifunctional as the bifunctional acrylic oligomer . 5. Electro-optical cross-linked polymer material that changes the refractive index when an electric field is applied, obtained by three-dimensional radical polymerization of a polymerization-capable acrylic composition according to any one of claims 1 to 4 during photochemical or thermal initiation. 6. A method of producing an electro-optical crosslinked polymeric material according to claim 5, comprising the step of preparing a polymerization-capable acrylic composition according to any one of claims 1 to 4 and the stage of curing it, consisting of the following operations:
1) dissolving an acrylic monomer containing an electron withdrawing moiety in a polymerization solvent monomer;
2) adding to the resulting solution an acrylic monomer containing an electron-donating moiety;
3) heating the resulting mixture at 40-50 ° C for 5-10 minutes;
4) adding to the resulting solution a bifunctional acrylic oligomer and a polymerization initiator and mixing until complete dissolution to obtain a composition;
5) the manufacture of a film of a given thickness from the resulting solution;
6) curing the resulting composition by photochemical or thermal initiation of three-dimensional radical polymerization with the formation of electro-optical cross-linked polymer material.