RU2402578C1 - Photochromic polymerisable composition, photochromic cellular optical material and method of obtaining said material - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: disclosed polymerisable photochromic composition contains: (1) 15-65 pts. wt silicate glass powder impregnated with an inorganic photochromic compound; (2) 100 pts. wt of a mixture of a radically polymerising compound containing an oligomer with two (meth)acrylic groups bonded by a divalent radical which does not contain aromatic groups, having refraction index lower than that of silicate glass which is impregnated with a photochromic compound, an oligomer with two (meth)acrylic groups bonded a divalent radical which contains aromatic groups, having refraction index which is greater than that of silicate glass impregnated with an inorganic photochromic compound. Disclosed also is a photochromic cellular optical material which is a product of solidification of the said photochromic composition, which retains not less than 90% optical transmission in the visible spectrum in temperature range of +/-20°C of the given ambient temperature, suitable for long-term use. Disclosed also is a method of producing said photochromic material, including in form of triplexes.

EFFECT: good working characteristics.

11 cl, 6 dwg, 5 tbl, 49 ex

Description

FIELD OF THE INVENTION

The present invention relates to a polymerization composition containing an inorganic photochromic compound, to a photochromic optical material and to a method for its preparation. More specifically, the invention relates to a photochromic polymerization composition containing an inorganic glass powder impregnated with an inorganic photochromic compound as filler, to a photochromic network optical material and to a method for its preparation, comprising curing said composition by three-dimensional radical polymerization on a sheet of transparent organic glass or between two sheets of transparent organic glass with the formation of photochromic duplex or tr Iplexa.

Photochromic triplexes based on organic glasses can be used in all fields of application of photochromic optical materials based on photochromic organic compounds and, moreover, also in products intended for long-term operation, for example, large-scale glass structures of buildings and sports facilities, greenhouses (adjustable insolation), space objects with controlled conductivity of insolation, (for example, the design of the base on the moon, etc.), glazing of window openings, airplane windows, protective x guards sports helmets, motorcycle windscreens, etc.

State of the art

Photochromic triplexes, duplexes and films based on polymer compositions containing a certain amount of an organic compound that changes color when exposed to light are currently known, usually due to a reversible chemical transformation, for example, a ring opening and recycling reaction. Methods for incorporating a photochromic organic compound into a polymer matrix include either coating or doping the matrix (US Application 2006/0033088):

- dissolving or dispersing the photochromic organic compound in the matrix by introducing the photochromic organic compound into the monomer before polymerization;

- impregnation or thermal diffusion of photochromic organic compounds into the matrix using solutions of the specified photochrome at high temperatures;

- the introduction of photochromic organic compounds as an individual layer between adjacent layers of the matrix, for example as a layer of a polymer film;

- the use of photochromic organic compounds as coatings on the surface of the matrix.

The most common composition of a photochromic organic compound with polymerization oligomers and monomers (US Patents 6,926,510, 5,910,516, 5,621,017; US Applications 2006/0023160, 2006/0055070, 2006/0033081; Europe. Pat. 1,433,814).

A common and fundamental drawback of all products based on photochromic organic compounds is the limited working life due to the irreversible photochemical conversion of substances. In some cases, for example for cheap sunglasses, the life of the product is acceptable (up to two years), but in most other applications, for example for lenses, protective screens, glazing elements of buildings and vehicles, in particular triplexes, a short operating time eliminates the use of photochromic organic compound.

In addition, photochromic organic compounds in polymerization compositions interact with initiators of photochemical or thermal curing, which degrades photochromic properties and impedes the process of forming the product [US Application 2006/0055070]. To eliminate this effect, one has to resort to a significant complication of the technology for producing the product.

On the other hand, photochromic silicate glasses, as is now well known, are characterized by the ability to darken under the action of actinic radiation, especially ultraviolet radiation, and to brighten when the radiation source is turned off. Photochromism in such glasses mainly develops as a result of the formation of the microcrystalline phase of silver halides (usually after thermal post-processing of glass). Since the invention of these glasses (US Patent 3,208,860) about 30 years ago, photochromic silicate glasses have been used with various variations in a large number of inventions, due to the need to optimize the given photochromic characteristics for each specific application, see, for example, the latest US Patents 6,177,371. 6165922, 6162749 and others. In general, the critical characteristics of photochromic glasses for ophthalmic applications include: their color (usually gray or brown), the level of image transmission in the initial state in the absence of irradiation and after staining when exposed to actinic radiation, the amplitude of the change in the level of image transmission in colored and unpainted form as a function of temperature in the range between 0 and 40 ° C and the rate of reversible bleaching after removal of the excitation source.

Glasses containing photosensitive AgCl microcrystals possess the best photochromic properties (e.g. Corning photochromic glasses: Photobrown® / Photogray® Extra, Photobrown® / Photogray® Sunsitive, Photobrown® 16/45, Photogray® 16, Photogray® Thin & Dark, XDF Dark Gray). Also developed (A.V. Dotsenko, L. B. Glebov, V. A. Tsekhomsky. "Physics and Chemistry of Photochromic Glasses". CRC Press. Boca Raton. N.-Y. 1998. 190 p.) PHG-5 photochromic glasses based on CuHal light-sensitive microcrystals. Unlike AgHal glasses, PHG-5 glasses darken not only under ultraviolet radiation, but also when exposed to visible or infrared light. These photochromic glasses have an almost unlimited shelf life for photochromic properties.

Despite the unique stability of photochromic silicate glasses, the practical use of these glasses is hindered by their heavy weight, the risk of eye damage when glass breaks, and high molding temperatures of the product (above 1000 ° C).

Disclosure of invention

The above disadvantages of both organic photochromic optical materials and inorganic photochromic glasses can be eliminated using hybrid silicate-polymer glasses, but such hybrid glasses have not yet been developed. Perhaps this is due to the need to solve very complex problems, both from the point of view of selecting the composition of the composition and characteristics of the filler, and the complexity of choosing the technology for creating a transparent product from two such heterogeneous components.

To solve this problem, it is fundamental to create a polymerization-capable acrylic composition (binder), which after curing forms a polymer with a refractive index identical to that of an inorganic glass impregnated with an inorganic photochromic compound.

An object of the present invention is to provide a polymerization-capable photochromic composition filled with silicate glass powder impregnated with an inorganic photochromic compound, which, after curing, forms a transparent hybrid optical material.

The objective of the invention is the creation of a photochromic network optical material with high performance characteristics: high transparency in the visible region of the spectrum, high speed and intensity of staining during irradiation, high speed of discoloration. It is especially important that the specified material will have an almost unlimited time for the conservation of photochromia, that is, the service life determined by the viability of the polymer matrix.

The objective of the invention is also the development of a method for producing photochromic network optical material, which will provide the resulting material with the above high performance.

The solution of the tasks is achieved by the proposed:

- Photochromic polymerization-capable composition, including:

(1) 15-65 wt. parts of silicate glass powder impregnated with an inorganic photochromic compound;

(2) 100 wt. parts of a mixture of radically polymerizable compounds containing: 40-70 wt. parts of an oligomer with two (meth) acrylic groups linked by a divalent radical containing no aromatic groups having a refractive index lower than that of silicate glass impregnated with an inorganic photochromic compound,

1-20 wt. parts of an oligomer with two (meth) acrylic groups linked by a divalent aromatic radical having a refractive index higher than the refractive index of silicate glass impregnated with an inorganic photochromic compound,

0-15 wt. plasticizer parts and

20-30 wt. parts of one or more vinyl monomers;

(3) 0.1-5.0 wt. parts of the polymerization initiator.

The specified powder of silicate glass impregnated with an inorganic photochromic compound may be glass microspheres, microcylinders or microfilaments of fractional composition from 50 to 350 microns, obtained in the process of melting in a furnace of utilized battle or industrial waste photochromic glass.

The specified silicate glass powder impregnated with an inorganic photochromic compound may be glass microspheres, microcylinders or microfilaments of fractional composition from 50 to 350 microns, obtained on a plasma torch installation with a uniform profile of the formation zone.

The specified oligomer with a refractive index below the refractive index of silicate glass impregnated with an inorganic photochromic compound may have the following structure:

where R ¹ = —H, —F or CH ₃ ;

R ² is a divalent group of the formula:

where R ³ = —H, —F or CH ₃ ; n is an integer from 0 to 10;

X is a divalent organic group with an ester, carbonate or urethane group of the formula: -YR ⁴ -Y-,

where Y is a divalent group —CO—, —COO—, —CONH — R ⁵ - or —R ⁵ NHCO—,

R ⁴ is a divalent organic group of the formula:

where n is an integer from 1 to 3, m is an integer from 1 to 250;

R ⁵ is a divalent organic group of the formula:

- (CH ₂ ) _n -,

where n = 2-8.

The specified oligomer with a refractive index below the refractive index of silicate glass impregnated with an inorganic photochromic compound may have the following structure:

where R ¹ = —H, —F or —CH ₃ ; n is an integer from 1 to 20; m = 0 or 1.

The plasticizer may have the following structure:

where R ¹ = - (CH ₂ ) ₂ OOCC (CH ₃ ) = CH ₂ and / or -CH (CH ₃ ) ₂ .

- A photochromic networked optical material, which is the product of the curing of the claimed photochromic polymerization composition during thermal or photochemical initiation of three-dimensional radical polymerization and having an optical transmittance in the visible region of the spectrum of at least 90% in the temperature range +/- 20 ° C of the specified ambient temperature.

The photochromic network optical material is preferably the product of curing the claimed composition on at least one surface of a sheet of transparent organic glass as a substrate to form a duplex or between two sheets of transparent organic glass to form a triplex, while as a transparent organic glass for a substrate, polymethyl methacrylate or polycarbonate should be used.

- A method for producing photochromic network optical material, comprising the following stages:

(1) preparing the claimed photochromic polymerization composition by mixing liquid components with silicate glass powder;

(2) applying the prepared composition to a transparent organic glass substrate;

(3) the implementation of three-dimensional radical polymerization of a composition deposited on a substrate by thermal or photochemical initiation.

Silicate glass powder is preferably pretreated with a solution of an adhesion promoter, followed by removal of the solvent and drying.

The mixing of the liquid components of the composition with silicate glass powder is preferably carried out at 40-50 ° C.

The proposed composition, optical material and method for its production have no analogues.

A brief description of the drawings.

Figure 1 shows the photochromic microspheres of silicate glass obtained from microchips of photochromic glass in the process of heat treatment.

Figure 2 shows the temperature dependence of the refractive index for oligomers and their compositions (composition in% wt.).

1. OUM-1 100;

2. OUM-1 90.8 + bis-PHA 9.2;

3. OUM-1 86.7 + bis-PHA 13.3;

4. OUM-1 84.8 + bis-PHA 15.2;

5. OUM-1 80 + bis-PHA 20;

6. bis-PHA 100;

7. OUM-1 35 + bis-PHA 35 + TsGMA 30;

8. OUM-1 34 + bis-PHA 18 + TsGMA 30 + Styrene 18;

9. OUM-1 55 + bis-PHA 20 + TsGMA 15 + PPM5S 10;

10. OUMP-1 55 + bis-PHA 20 + TsGMA 15 + PPM5S 10;

11. OUMP-2 55 + bis-PHA 20 + TsGMA 15 + PPM5S 10;

12. Photochromic glass "Photogrey Extra ™" company Corning (USA).

Figure 3 shows the temperature dependence of the refractive index (n ²⁰ D) for polymers obtained by curing some unfilled compositions.

1-4. Compositions OUM-1 and bis-PHA containing 9.2, 13.3, 15.2 and 20% wt. bis-PHA.

5. The composition of OUM-1 34% + bis-PHA 18% + TsGMA 29% + styrene 18%.

6. The composition of OUM-1 35% + bis-PHA 35% + TSGMA 29%.

The horizontal line with n = 1.524 is the refractive index of photochromic glass "Photogrey Extra ™" company Corning (USA).

Figure 4 shows the change in the transparency of polycarbonate triplexes at a temperature of optical uniformity (in the center) and 30 ° C above (left) and below this temperature (right).

Figure 5 demonstrates the performance of polycarbonate triplexes - the change in transmission before (right) and after exposure to sunlight (left).

Figure 6 shows the change in transparency of the polycarbonate triplex preform before polymerization of the inner layer (right) and after curing.

The implementation of the invention

The creation of the invention required a large amount of experimental research. The composition of the binder - a mixture of polymerization-capable acrylic compounds - should provide the polymer obtained by curing with a refractive index identical to that of the filler - photochromic silicate glass. An additional complication lies in the fact that during the polymerization the refractive index of the binder changes and in order to maintain the proximity of the refractive indices of the binder and the filler, it was necessary to maximize the consumption of double bonds in the components of the binder during curing. In addition, the refractive index of polymers is quite dependent on temperature, so a study was made of the influence of the composition of the composition on the temperature coefficient of the refractive index of the resulting optical material. This made it possible to select compositions with a minimum temperature coefficient of refractive index, which ensured that the transparency of the proposed optical material was maintained in the range of at least +/- 20 ° C from a given ambient temperature.

The next problem requiring experimental research was the determination of the optimal size and shape of the filler particles - photochromic silicate glass to achieve good binder wettability and the necessary degree of filling while maintaining the transparency of the optical material.

Finally, when developing a method for producing optical material, it was necessary to overcome such problems as the formation of difficult to remove air inclusions and settling of the filler during processing, which are characteristic of the distribution of finely dispersed filler in a viscous matrix with a large difference in the density of components.

The studies performed allowed us to solve the above problems.

Table 1 presents the abbreviations of the most commonly used components of the claimed composition.

It was found that any radically polymerizable compound can be used as an oligomer with a low refractive index - lower than the refractive index of silicate glass impregnated with an inorganic photochromic compound if it contains two (meth) acrylic groups linked by a divalent radical without aromatic groups.

A typical example of an oligomer with a low refractive index is an oligomer of structure (I):

where R ¹ = —H, —F or CH ₃ ;

, в которой R³=-H, -F или -СН₃; n - целое число от 0 до 10;R ² is a divalent group:

wherein R ³ = —H, —F, or —CH ₃ ; n is an integer from 0 to 10;

X is a divalent organic group with an ester, carbonate or urethane group of the formula: -YR ⁴ -Y-,

where Y is a divalent group —CO—, —COO—, —CONH — R ⁵ - or —R ⁵ NHCO—,

R ⁴ is a divalent organic group:

where n is an integer from 1 to 3, m is an integer from 1 to 250;

R ⁵ is a divalent organic group:

where n = 2-8.

Preferred oligomers of structure (I) with a low refractive index are represented by compounds of formula (1) (OUM-1), (2) (OUM-2) and (3) (OUM-3):

where: (1) R ¹ = CH ₃ , R ² = H, n = 0, m = 15-20 (OUM-1); (2) R ¹ = H, R ² = CH ₃ , n = 3-5, m = 15-20 (OUM-2); (3) R ¹ = CH ₃ , R ² = CH ₃ , n = 3-5, m = 15-20 (OUM-3).

Compounds (1) - (3) were synthesized by the reaction of macrodiisocyanate based on oligotetrahydrofuran-α, ω-diol with a molecular weight of about 1400 with ethylene glycol monomethacrylate (MEG) - OUM-1, or with monoacrylate (Bisomer ™ PPA5S) - OUM-2, or with polyoxypropylene glycol monomethacrylate (Bisomer ™ PPM5S) - OUM-3.

Other examples of low refractive index oligomers besides those presented above include polyalkylene glycol di (meth) arylates, such as polyethylene glycol di (meth) acrylates with an average molecular weight of 300-1500 (hereinafter (meth) acrylate means that this term refers to to acrylates and methacrylates), polypropylene glycol di (meth) acrylates with an average molecular weight of 375-700, polytetramethylene glycol di (meth) acrylates with an average molecular weight of 500-1500 and perfluoroheptylene ethylene glycol di (meth) acrylates with an average molecular weight of 500- 600.

Any radically polymerizable compound can be used as an oligomer with a high refractive index — higher than the refractive index of silicate glass impregnated with an inorganic photochromic compound if it has two (meth) acrylic groups linked by a divalent radical containing aromatic groups.

A typical example of an oligomer with a high refractive index can be represented by structure (II):

where R ¹ = —H, —F or CH ₃ ; n is an integer from 1 to 20; m = 0 or 1.

Preferred oligomers of structure (II) with a high refractive index are bis-GMA and its ethoxylated and glycerated analogues of formulas (4), (5) and (6), respectively.

The polymerization composition of this invention may include an acrylic plasticizer in addition to the aforementioned low and high refractive index bifunctional oligomers. This is preferable from the point of view of achieving optimal characteristic properties, such as the density of the three-dimensional network of the polymer and, therefore, the elasticity of the network optical polymer.

The plasticizers used in this invention are acrylic oligomers of structure III, that is, they are analogues of an oligomer of structure (I) without one or both (meth) acrylic groups:

where R ¹ = - (CH ₂ ) ₂ OOCC (CH ₃ ) = CH ₂ and / or -CH (CH ₃ ) ₂ .

These compounds were obtained by the method developed for the synthesis of OUM-1, but with the replacement of 0.33 or 0.66 or 1 mole of telogen (MEG) with an equimolecular amount of non-polymerization isopropanol (plasticizers OUMP-1, OUMP-2 and OUMP-3, respectively )

The polymerization composition of this invention also includes radically polymerizable vinyl monomers. This is important from the point of view of regulating the viscosity of the composition and achieving the necessary physical and mechanical properties of the resulting cured product.

The choice of radical polymerizable vinyl monomers is practically unlimited, and any known compounds having a radical polymerizable group, such as (meth) acryloyl, (meth) acryloyloxy, vinyl, allyl or styryl, can be used. Of the radical polymerizable monomers, compounds with (meth) acryloyl or (meth) acryloyloxy groups are most preferred in terms of polymerization speed and availability.

The monomers used in the claimed composition include unsaturated carboxylic acids and their derivatives, such as methyl methacrylate, butyl methacrylate, benzyl (meth) acrylate, 2-hydroxyethyl methacrylate and hydroxypropylene glycol monomethacrylate; methylthioacrylate, benzylthioacrylate and benzylthiomethacrylate, as well as styrene, α-chlorostyrene, α-methylstyrene, α-bromostyrene and N-vinylpyrrolidone.

Obtaining a photochromic crosslinked product by three-dimensional free radical polymerization of the proposed composition can be carried out using any of the known methods of initiation - thermal, photochemical using light wavelength from the ultraviolet region to ~ 550 nm, or α-, β- or γ-radiation, or a combination of the above methods, in this case, many of the known initiators of radical polymerization can be used.

Typical examples of a thermal polymerization initiator include diacyl peroxides, such as benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide and acetyl peroxide; peroxyesters such as tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydicarbonate, cumyl peroxyneodecanoate and tert-butyl peroxybenzoate; percarbonates such as diisopropyl peroxydicarbonate, di-2-ethylhexylperoxydicarbonate and di-sec-butyloxycarbonate; azo compounds such as 2,2'-azo-bis-isobutyronitrile (AIBN), 2,2'-azobis (4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile) and 1,1'-azobis (cyclohexane -1-carbonitrile).

The amount of thermal polymerization initiator depends on the polymerization conditions, type of initiator, composition, and structure of the components. Thermal polymerization initiators can be used either separately or as a combination of two or more compounds.

Among the compounds generating free radicals when irradiated with ultraviolet light, benzoin, benzoin methyl ether, benzoin butyl ether, benzophenone, acetophenone, 4,4'-dichlorobenzophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1 can be used as photopolymerization initiators. -phenyl-propan-1-one, benzyl methyl ketal, 1- (4-iso-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-isopropylthioxantone, bi (2,6-dimethoxy- benzoyl-2,4,4-trimethylpentyl) phosphine, bi (2,4,6-trimethylbenzoyl) phenylphosphine oxide, about 2,4,6-trimethylbenzoyldiphenylphosphine sulfoxide or 2-benzyl-2-dimethyl-amino-1- (4-morpholinophenyl) -1 -butanon.

It is possible to use either one or a combination of two or more photoinitiators.

In the following illustrative examples, a mixture (1: 1 by weight) of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and 2-hydroxy-2-methylpropiophenone (hereinafter referred to as FI) was used.

When carrying out photo-curing of the claimed composition after UV irradiation in the presence of a photoinitiator to complete the polymerization, you can additionally conduct heat treatment at 60-85 ° C.

For UV irradiation, any known UV light source can be used, for example, a high pressure mercury lamp, superhigh pressure mercury lamp, low pressure mercury lamp, xenon lamp, carbon arc, antibacterial lamp, metal halide lamp and electrodeless lamps. The exposure time of one of the listed light sources is determined by the type of lamp, the absorption wavelength and sensitivity of the initiator of photopolymerization, as well as the thickness of the polymerized layer.

In most of the examples below, a 1000 W high pressure mercury lamp (DRT-1000) was used for photochemical initiation.

To initiate the polymerization, it is possible to use a mixture of a photoinitiator with a thermal polymerization initiator.

To implement the present invention, the choice of photochromic inorganic glass powder is not particularly limited and any known inorganic glass impregnated with any known inorganic photochromic compound can be used.

Illustrative examples include the use of CorHing® Photogrey Extra ™ AgHal-containing silicate glasses (USA) with a refractive index of n = 1.524 or PHG-5 CuHal-containing silicate glasses (GOI, Russia), n = 1.499.

It has been found that in order to improve the operational properties of the cured filled optical material, such as transparency and adhesion, it is preferable to use spherical photochromic filler particles, for example microspheres. The spherical shape of the particles makes it possible to obtain high-quality optical material with enhanced adhesion between the binder and the filler, while triplexes are characterized by good photochromic properties of the inner layer. The spherical shape of the glass particles is also optimal for the process of preparing a polymerization-capable composition (for the filling process), which allows achieving very high degrees of filling of the optical material. Anisodiametric powder particles, for example microcylinders and microfilaments, which are not stress concentrators, but, on the contrary, act as reinforcing elements that strengthen the polymer matrix, can also be used.

The particle size of the filler can vary in the range from 50 to 350 microns, in which case a high-quality photochromic optical material is obtained.

To improve the adhesion of the filler to the three-dimensional cross-linked polymer, it is preferable to pre-treat the surface of the glass microparticles with an adhesion promoter, using any known adhesion promoters for silicate glasses, for example 3- (trimethoxysilyl) propyl methacrylate (0.5% solution in ethanol). This compound forms fairly tight chemical bonds with silicate glass due to partial hydrolysis, and is also capable of copolymerization with the components of the composition due to the presence of an acrylic group.

Any transparent sheet material can serve as a substrate for producing the photochromic network optical material of the present invention, but typical organic glasses, such as polymethyl methacrylate or polycarbonate sheets from 0.1 to 2 mm thick, most preferably 0.5-2.0 thick, are most preferred. mm

Table 2 shows the contact refractometric characteristics: refractive indices (n _D) and temperature coefficients of refractive index (δn) of certain basic components of the composition and products of their curing - homopolymers: n ²⁰ _ref, n ²⁰ _holes, δn _ref, δn _holes and the magnitude Δn = n ²⁰ _holes -n ²⁰ _ref . Oligomers of structures I and II have a fairly wide range of refractive indices (see FIG. 2), therefore, it is possible to obtain a composition with a given refractive index — for example, the refractive index of a filler — inorganic glass. Low values Δn typical of all studied homopolymers and magnitude Δn _{of holes} close to the parameters oligomers. This means that the curing of oligomers of structure I and II is accompanied by a very low shrinkage and, consequently, the absence of significant internal stresses in the network three-dimensional optical material, including at the interface matrix-filler.

Values δn _holes for cross-linked polymers of structure (II) (1.87 · 10 ^-4 and 1.3 × 10 ^-4 for polymers Bis-Bis-PEA and PHA respectively) lower than OUM polymers, since these polymers have smaller thermo-optic effect. At the same time, the structure II oligomers have δn _ref and Δn (Δn = 0.0159) close to the OAM parameters, and such a correlation of refractometric parameters for oligomers with low and high refractive indices indicates close shrinkage values during the polymerization of structure oligomers (I ) and (II).

Table 3 shows the refractometric characteristics for unfilled acrylic binders and cross-linked polymers based on them. From these data it can be seen that all the original binders, regardless of their refractive index, are characterized by the same (within the measurement error) value of the temperature coefficient of the refractive index δn _ex ~ 3.8 ± 0.2 · 10 ^-4 . Polymers have an even lower temperature coefficient of refractive index, while the refractive index of the studied polymers lies in a rather wide range, which makes it possible to use various grades of glass as a filler.

All investigated refractometric characteristics are very significant, because they determine the temperature of the optical uniformity of the claimed photochromic optical material (T _one ).

Figure 3 shows the temperature dependence of the refractive index of the polymers obtained by curing some unfilled oligomers and their compositions in the temperature range 15-65 ° C. For the present invention, only polymers are used for which this dependence crosses the straight line for the filler, parallel to the temperature axis, i.e. the conditions of optical uniformity of the filled matrix will be realized (see Fig. 4). The temperatures of the intersection points found in this way coincided with the temperatures obtained by an independent thermo-optical method, fixing the optical uniformity of the photochromic network optical material in the microscope field.

The proposed photochromic network optical material is obtained as follows.

First, all liquid components of the composition are mixed: polymerization compounds and a polymerization initiator.

Then, a filler is added to the liquid binder, a finely divided photochromic silicate glass powder having a fractional composition from 50 to 350 microns. The surface of the filler particles is preferably pre-treated with an alcohol solution of the adhesion promoter. Then the solvent is removed and the glass powder is dried at 60 ° C. to constant weight.

Mixing a binder with a glass powder is preferably carried out at 40-50 ° C.

The prepared photochromic composition is applied to the surface of a sheet of organic or silicate glass, limited by laying a predetermined thickness. In the case of the manufacture of triplex, a second sheet of organic glass is placed over the liquid layer of the composition and the assembled triplex preform is fixed with clamps.

The photochromic polymerization composition deposited on the surface of the substrate is cured by three-dimensional radical polymerization by thermal or photochemical initiation.

The claimed method obtained photochromic network optical material, characterized by a temperature of achieving optical uniformity (T _one ) in the range of 10-40 ° C and a rather low thermal coefficient of refractive index - not higher than 3.0 · 10 ^-4 deg ^-1 . Any temperature shift from T _alone reduces the optical uniformity of the system, that is, the light transmission of the photochromic material decreases (see Fig. 4). The temperature mode of operation of the proposed material is thus determined by a given amount of light transmission. The greater the amount of light transmission required when using optical material, the more narrow the temperature range its operation is possible.

The following examples more specifically describe the essence of the present invention, but do not limit possible embodiments of the invention.

Synthetic example A. Synthesis of oligourethane methacrylate structure (1) - OUM-1.

500 g (0.5 mol) of oligotetrahydrofuran-α, ω-diol of diisocyanate (Mn≈1000), 140.8 g (1.1 mol) of ethylene glycol monomethacrylate (MEG) and 9.0 g of tin dilaurate are stirred at room temperature for 12 hours to complete consumption of isocyanate groups in the IR spectra. The output is ~ 100%. M _n ≈1400; M _w ≈1600; M _w / M _n ≈ 1.2; functionality ~ 2, d ₄ ²⁰ = 1086 kg m ^-3 , n ²⁰ _D = 1,5027.

Synthetic examples B and C. Synthesis of oligourethane methacrylates of structures (2) and (3) - OUM-2 and OUM-3.

Oligourethane methacrylates of structures (2) and (3) are obtained from 500 g (0.5 mol) of oligotetrahydrofuran-α, ω-diol of diisocyanate according to the procedure of Synthetic Example A using instead of MEG 1.1 moles of telogen - “Bisomer ™” PPA5S (423.6 g ) or "Bisomer" PPM5S ™ (398.2 g), respectively.

Synthetic examples GE. Synthesis of plasticizers OUMP-1, OUMP-2 and OUMP-3.

Plasticizers are prepared from 500 g (0.5 mol) of oligotetrahydrofuran-α, ω-diol of diisocyanate according to the procedure of Synthetic Example A using instead of MEG 1.1 moles of isopropanol or a mixture of telogens: MEG and isopropanol:

Structure (4) (OUMP-1): 0.73 MEG and 0.37 mol of isopropanol.

Structure (5) (OUMP-2): 0.37 MEG and 0.73 mol of isopropanol.

Structure (6) (OUMP-3): 1.1 moles of isopropanol.

Preparation of unfilled polymerization binders and their curing.

Example 1

55.0 g OUM-1, 19.9 g Bis-PHA, 9.0 g PPM5S, 15.0 g CHMA and 1.1 g PHI are mixed in a dark glass glass vessel. The resulting binder containing a photoinitiator is polymerized under UV irradiation (1000 W Hg lamp) for 4 minutes.

The refractometric characteristics of the binder and the unfilled three-dimensional network optical polymer obtained by curing it are shown in Table 3.

Examples 2-12.

Binders are prepared according to the procedure of Example 1. Qualitative and quantitative composition, curing conditions, and refractometric characteristics of the initial binders and polymers are shown in Table 3.

Preparation of a filled photochromic polymerization composition.

Example 13

39.45 g of OUM-1, 20.17 g of Bis-PHA, 9.42 g of PPM5S, 15.65 g of CHMA, 14.36 g of OUMP-3 and 0.947 g of PHI are mixed in a dark glass glass vessel. 100 g of a liquid binder are obtained.

Filler - powder of photochromic silicate glass "Photogrey Extra ™" from Corning (USA), impregnated with AgCl, with a particle size of 0.16-0.25 mm (160-250 microns) is pre-treated in the following sequence: screening of the small fraction, multiple decantation first in water and then in ethanol, the introduction of a 0.5% solution of the adhesion promoter - 3- (trimethoxysilyl) propyl methacrylate in ethanol, removing the solvent and drying the filler at 60 ° C to constant weight.

40.06 g of a filler heated to 40-50 ° C are added in small portions to 100 g of a liquid binder, also heated to 40-50 ° C. Get 140.06 g of filled photochromic polymerization composition of the following composition:

wt. parts wt.% Photochromic Silicate Glass Powder 40.06 28.60 Radically polymerizable compounds 99.05 70.72 Polymerization initiator 0.95 0.68

In this case, the radically polymerizable compounds have the following composition in wt. parts:

Low refractive index oligomer (OUM-1) 39.45 High Refractive Index Oligomer (Bis-FGA) 20.17 Acrylic plasticizer (OUMP-3) 14.36 Vinyl monomers (PPM5S - 9.42; TsGMA - 15.65) 25.07

The resulting filled photochromic polymerization composition is translucent in close examination, but the filler particles are visible in the light. It should be noted that the initial compositions should not be completely transparent, since during polymerization, the refractive index increases by 1-2 units in the second sign, and this effect was taken into account when selecting the composition of the composition — full transparency is achieved after curing (see Fig. 6) . Characteristics of the resulting filled composition are shown in Table 4.

Examples 14-24.

The filled composition is obtained according to the method of Example 13. Qualitative and quantitative compositions of the composition and its characteristics are shown in Table 4.

Obtaining photochromic network optical material by photochemically initiated polymerization.

Example 25

The polymerization photochromic composition shown in Example 13 is irradiated with a 1000 W Hg high-pressure lamp for 4 minutes on the surface of organic or silicate glass.

In some cases, additional heating was used at 45 ° C for 10-15 minutes to complete three-dimensional polymerization.

The conditions for obtaining the mesh material and its properties are given in Table 5.

Examples 26-35.

A photochromic polymerization-capable composition, the composition and properties of which are shown in Examples 14-24, is processed according to the procedure of Example 25 to obtain a photochromic network optical material, the conditions for obtaining the material and properties are given in Table 5.

Example 36. Obtaining photochromic network optical material of thermally initiated polymerization.

The liquid polymerization composition shown in Example 24 is heated at 85 ° C. for 30 minutes on the surface of an organic or silicate glass. The conditions for obtaining the material and properties are given in Table 5.

Obtaining polycarbonate photochromic triplexes by photochemically initiated polymerization.

Example 37

The polymerization photochromic composition described in Example 13 was processed according to the procedure described in Example 25, but between two sheets of polycarbonate glass.

Some properties of the obtained triplex are given in Table 5.

Examples 38-47.

Polymerization photochromic compositions described in Examples 14-23, respectively, were cured by the method described in Examples 26-35, but between two sheets of polycarbonate glass.

Some properties of the obtained triplexes are given in Table 5.

Example 48

Obtaining polycarbonate photochromic triplex by thermally initiated polymerization.

The polymerization photochromic composition described in Example 24 was processed according to the procedure of Example 36, but between two sheets of polycarbonate glass. Some properties of the obtained triplex are given in Table 4.

Example 49

Preparation of a photochromic polymerization-capable composition filled with photochromic CuHal-containing silicate glass of the PHG-5 brand (GOI, Russia), and its combined (photochemical and thermal) curing to obtain a photochromic network optical material and photochromic triplex.

56.13 g OUM-3, 13.0 g BZMA, 8.8 g PPM5S, 20.5 g OUMP-3, 0.82 g PHI and 0.75 g AIBN are mixed in a dark glass glass vessel. 100 g of a liquid binder are obtained with n ²⁰ _D = 1.4880.

Filler - photochromic silicate PHG-5 powder based on CuHal photosensitive microcrystals (GOI, Russia) with a refractive index of n ²⁰ _D = 1,499, with a particle size of 0.20-0.35 mm, is pre-processed according to the method described in Example 13.

50.0 g of a filler heated to 40-50 ° C are added in small portions to 100 g of a liquid binder, also heated to 40-50 ° C.

The resulting filled photochromic polymerization composition is translucent.

The prepared filled composition is applied to the surface of a polycarbonate glass sheet and irradiated with a 1000 W high-pressure Hg lamp for 4 min and then heated at 70 ° C for 4 min. Get photochromic network optical material having significant turbidity.

With a similar curing of the composition between two polycarbonate glasses, a photochromic triplex with low transparency was obtained.

Thus, a photochromic polymerization-friendly composition is developed, filled with photochromic silicate glass powder, which forms a transparent photochromic hybrid optical material after curing (see FIG. 5). The proposed photochromic three-dimensional network optical material obtained from the claimed composition combines excellent photochromic properties that are retained during long-term use: a sufficient intensity of dyeing during irradiation and a high rate of discoloration, as well as good optical properties such as colorlessness and transparency. The material retains at least 90% of the optical transmittance in the visible spectral range in the temperature range +/- 20 ° C at ambient temperatures from 10 to 40 ° C. In addition, three-dimensional mesh materials have high elasticity and impact strength, resistance to solvents, hardness, heat resistance, which makes it very promising to use the proposed optical material to obtain coatings on various substrates or as an inner layer of triplexes for various purposes. A method has been developed for producing the claimed photochromic network optical material, which provides the resulting material with the high operational characteristics listed above.

Table 1 Structures and abbreviations of the components of the composition Structure MEG Ethylene glycol monomethacrylate OUM-1 Oligourethane methacrylate from MEG and macrodiisocyanate based on oligotetrahydrofuran-α, ω-diol and toluene diisocyanate. (Synthetic example A) OUM-2 OUM-3 Oligourethane methacrylate from Bissomer PPA5S or Bissomer PPM5S and a macrodiisocyanate based on oligotetrahydrofuran-α, ω-diol and toluene diisocyanate. (Synthetic examples B and C) OUMP-1 Monoisopropoxy oligourethane monomethacrylate is an OUMA analog obtained using a mixture of MEG and isopropanol in a ratio of 0.66: 0.33. (Synthetic example G) OUMP-2 Monoisopropoxy oligourethane monomethacrylate is an OUMA analog obtained using a mixture of MEG and isopropanol in a ratio of 0.33: 0.66. (Synthetic example D) OUMP-3 Diisopropoxy oligourethane from oligotetrahydrofuran-α, ω-diol and macrodiisocyanate based on isopropanol and toluene diisocyanate. (Synthetic example E) Bis-GMA Bisphenol A diacrylate Bis-FEA Ethoxylated Bisphenol A Diacrylate Bis-FGA Bisphenol A Glycerolate Diacrylate PPM5S Bisomer PPM5S ™ (Polyoxypropylene Glycol Monomethacrylate) Bzma Benzyl methacrylate TsGMA Cyclohexyl methacrylate OMA Octyl methacrylate N-VP N-vinylpyrrolidone FI Photoinitiator: mixture (1: 1 by weight) diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and 2-hydroxy-2-methylpropiophenone AIBN Azo bis isobutyronitrile

Claims (11)

1. Photochromic polymerization composition, including:
(1) 15-65 parts by weight silicate glass powder impregnated with an inorganic photochromic compound;
(2) 100 parts by weight mixtures of radically polymerizable compounds containing:
40-70 parts by weight oligomers with two (meth) acrylic groups linked by a divalent aromatic-free radical having a refractive index lower than that of silicate glass impregnated with an inorganic photochromic compound,
1-20 parts by weight oligomers with two (meth) acrylic groups linked by a divalent aromatic radical having a refractive index higher than the refractive index of silicate glass impregnated with an inorganic photochromic compound,
0-15 parts by weight plasticizer and
20-30 parts by weight one or more vinyl monomers;
(3) 0.1-5.0 parts by weight polymerization initiator. 2. The photochromic polymerization composition according to claim 1, characterized in that said silicate glass powder impregnated with an inorganic photochromic compound is glass microspheres, microcylinders or microfilaments of fractional composition from 50 to 350 microns, obtained during reflow in an utilized battle or industrial furnace photochromic glass waste. 3. The photochromic polymerization composition according to claim 1, characterized in that said silicate glass powder impregnated with an inorganic photochromic compound is glass microspheres, microcylinders or microfilaments of fractional composition from 50 to 350 microns, obtained on a plasma torch with a uniform profile of the formation zone. 4. Photochromic polymerization composition according to claim 1, characterized in that said oligomer with a refractive index lower than the refractive index of silicate glass impregnated with an inorganic photochromic compound has the following structure:

where R ¹ = —H, —F or —CH ₃ ;
R ² is a divalent group of the formula:

where R ³ = —H, —F or —CH ₃ ; n is an integer from 0 to 10;
X is a divalent organic group with an ester, carbonate or urethane group of the formula:
-YR ⁴ -Y-,
where Y is a divalent group —CO—, —COO—, —CONH — R ⁵ -, or —R ⁵ NHCO—,
R ⁴ is a divalent organic group of the formula:

where n is an integer from 1 to 3, m is an integer from 1 to 250;
R ⁵ is a divalent organic group of the formula:
- (CH ₂ ) _n -,

,
where n = 2-8. 5. Photochromic polymerization composition according to claim 1, characterized in that said oligomer with a refractive index higher than the refractive index of silicate glass impregnated with an inorganic photochromic compound has the following structure:

where R ¹ = —H, —F or —CH ₃ ; n is an integer from 1 to 20; m = 0 or 1. 6. Photochromic polymerization composition according to claim 1, characterized in that the plasticizer has the following structure:

where R ¹ = - (CH ₂ ) ₂ OOCC (CH ₃ ) = CH ₂ and / or —CH (CH ₃ ) ₂ . 7. Photochromic network optical material, which is the product of the curing of a photochromic polymerization-capable acrylic composition according to any one of claims 1 to 6 upon thermal or photochemical initiation of three-dimensional radical polymerization and which retains at least 90% optical transmittance in the visible spectrum in the temperature range +/- 20 ° C from the set ambient temperature. 8. The photochromic network optical material according to claim 7, characterized in that it is a curing product on at least one surface of a sheet of transparent organic glass as a substrate with the formation of duplex or between two sheets of transparent organic glass with the formation of triplex, while Polymethyl methacrylate or polycarbonate was used as transparent organic glass for the substrate. 9. A method of obtaining a photochromic network optical material, comprising the following stages:
(1) preparing a photochromic polymerization composition according to any one of claims 1 to 6 by mixing liquid components with silicate glass powder;
(2) applying the prepared composition to a transparent organic glass substrate;
(3) the implementation of three-dimensional radical polymerization of a composition deposited on a substrate by thermal or photochemical initiation. 10. The method of producing photochromic network optical material according to claim 9, characterized in that the silicate glass powder is pre-treated with a solution of an adhesion promoter, followed by removal of the solvent and drying. 11. The method of producing photochromic network optical material according to claim 9, characterized in that the mixing of the liquid components of the composition with silicate glass powder is carried out at 40-50 ° C.

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