RU2373061C1 - Photochromic organic triplexes and method of producing said triplexes - Google Patents

Abstract

FIELD: physics.

SUBSTANCE: photochromic triplex consists of two sheets of organic glass which are joined together by a photochromic cross-linked polymer, obtained from radical polymerisation of a photochromic acrylic composition. The acrylic composition is prepared by mixing liquid oligomers with two (meth)acrylic groups, with a flexible oligomer block and a rigid oligomer block, and a photochromic organic compound with subsequent introduction of a polymerisation initiator. The required amount of photochromic acrylic composition is poured into a mould made from two sheets of organic glass and the composition undergoes three-dimensionsl radical polymerisation with thermal or photochemical initiation.

EFFECT: triplexes with an elastic and strong inner layer also have good photochromic and optical properties.

10 cl, 9 tbl

Description

SUMMARY OF THE INVENTION

The present invention relates to photochromic triplexes based on organic glasses and a network photochromic optical polymer resulting from the radical polymerization of a polymerization photochromic acrylic composition. More specifically, the present invention relates to triplexes consisting of two sheets of organic glass, which are interconnected by a photochromic network polymer obtained by radical polymerization of said acrylic composition, and also to a method for producing said triplexes. Triplexes are intended for the manufacture of various types of glazing parts capable of discoloration during irradiation.

Prototype description

A lot of studies are known aimed at developing means of protecting the human eye from undesirable effects of bright light through the use of photochromic properties of glasses.

This is especially true for eyeglass lenses, which give photochromic properties either by introducing a photochromic compound into the lens material or by applying a photochromic coating to the surface of silicate or organic glass (for example, US Patent Nos. 6,114,437, 5,882,556, 6,797,104, 6,773,108). Photochromic coatings have also been proposed for the manufacture of goggles and eye protection devices, such as sports or fashion items, shields and helmets for general, industrial, or aviation applications (US Application 2006/0023160), for rear view mirrors, or car side mirrors (US Application 2006/0033088). Optical elements for goggles and eye protection can be made of silicate glass, hard plastics, polyurethane, organic glass - polymethyl methacrylate or polycarbonate, or other suitable material. Polycarbonate lenses are widespread in the United States, and the demand for impact-resistant sunglasses is growing rapidly due to high solar activity.

Coating compositions are typically mixtures of monomers and oligomers to which a photochromic organic compound is added. These compositions cure when exposed to heat and / or light, forming a coating with photochromic properties (for example, US Patent Nos. 5,882,556, 6,835,844, 6,602,603 and 6,362,248).

However, in the process of applying a composition containing a photochromic organic compound to one side of an organic glass substrate, it is difficult to obtain a smooth coating surface and control the film thickness. In the case of spectacle lenses, this effect leads to image distortion (US Patent No. 6,797,383). Moreover, the usual components of the coating compositions are (meth) acrylic compounds, the curing of which is inhibited by atmospheric oxygen, which makes it rather difficult to obtain coatings, especially thin ones, without surface stickiness.

The closest analogue of the present invention is US Pat. located between two transparent sheets of organic glass (US Patent 6,986,946). A significant drawback of the proposed solution is the in situ polyurethane synthesis reaction, i.e. in an article for a difficultly controlled polycondensation reaction between hygroscopic and hazardous diisocyanates and polyols, as well as the use of an inert solvent to be removed further (US Patent 6,986,946).

Thus, to date, high-quality photochromic triplexes based on organic glasses, obtained by commercially acceptable technology, have not been described.

The present invention solves the above problems.

SUMMARY OF THE INVENTION

An object of the present invention is a photochromic triplex based on organic glasses, consisting of two sheets of optically transparent glass, interconnected by a photochromic network polymer obtained by radical polymerization of an acrylic composition.

Another subject of the present invention is a reticulated photochromic optical polymer formed by three-dimensional polymerization of said acrylic composition on an organic glass substrate.

The subject of the present invention is also a polymerization composition of acrylic oligomers containing a photochromic compound.

Another subject of the present invention is a process for producing photochromic triplex by thermally and / or photochemically initiated radical polymerization of said acrylic composition between organic glasses.

The subject of the present invention is also the process of applying a protective coating to the surface of organic glass.

Other objects of the present invention and their advantages will be given below.

According to the present invention, firstly, the aforementioned objects and advantages of the existing invention are polymerization-capable acrylic compositions consisting of:

(1) 100 mass. parts of (meth) acrylic compounds (hereinafter (meth) acrylate means that this concept applies to both acrylates and methacrylates) capable of polymerization by a radical mechanism;

(2) 0.01 to 10 mass. parts of a radical polymerization initiator;

(3) 0.01 - 15 mass. parts of the photochromic compound.

According to the present invention, secondly, the aforementioned objects and advantages of the present invention are photochromic network optical polymers obtained by curing said polymerization composition.

According to the present invention, thirdly, the aforementioned objects and advantages of the present invention are photochromic triplexes, which are two sheets of organic glass, interconnected by a photochromic network optical polymer obtained by radical polymerization of the specified acrylic composition.

According to the present invention, fourthly, the aforementioned objects and advantages of the present invention are achieved by the process of producing photochromic triplexes, comprising applying a layer of a given thickness of the curable composition to the surface of organic glass, coating this layer with a second organic glass, fixing the structure with clamps and curing the inner layer when exposed to light, or when heated or when exposed to light and heat.

According to the present invention, finally, the above objects and advantages of the present invention are achieved by the process of applying a protective coating on one surface of a sheet of organic glass to prevent the polymer from swelling in contact with the polymerization-capable acrylic composition.

The developed photochromic triplexes based on organic glasses can be used in all known fields of application of photochromic optical materials, especially for glazing window openings, airplane windows, protective flaps of sports helmets, motorcycle wind flaps, etc.

Detailed Description of Preferred Option

To solve the problem of manufacturing high-quality photochromic triplex, the authors conducted an extensive study. As a result, the main factors are found that affect the optical, mechanical, and operational properties of the triplex.

The first factor that determines the quality of triplex is the chemical structure of acrylic compounds (oligomers and monomers), which should exclude possible specific reactions with photochromic compounds, especially during curing.

The second factor affecting the quality of the triplex is the method of initiation of three-dimensional radical polymerization, which determines the initiation rate, concentration of free radicals, rate constants of the polymerization process, and, most importantly, on the contribution of reactions of free radicals with a photochromic compound.

The third factor that determines the quality of triplex is associated with the effect of a polymerization-capable acrylic composition on the surface of a sheet of organic glass - the possibility of swelling of the polymer of which the glass is made, and some decrease in the optical properties of the triplex.

In connection with the foregoing, one objective of the invention is the synthesis of monomers and oligomers suitable for the preparation of a polymerization-capable photochromic acrylic composition, that is, without any effect of the components on the activity of the photochromic compound.

Another objective of the invention is to create a polymerization photochromic acrylic composition with the necessary physical parameters: viscosity, thixotropy, transparency.

Another objective of the invention provides for the creation of a network photochromic optical polymer by radical three-dimensional polymerization of the specified acrylic composition during photo- and / or thermal initiation with the necessary physical parameters: adhesion to a sheet of organic glass, elasticity, mechanical strength, impact strength and other properties characteristic of the inner layer ordinary triplexes.

Another objective of the invention is to provide a protective coating on the surface of a sheet of organic glass and its application process to prevent glass swelling.

Another objective of the invention provides for the creation of photochromic triplex from two sheets of organic glass and a reticulated photochromic optical polymer.

The aim of the invention is also the development of a process for producing photochromic triplex by three-dimensional radical polymerization of a polymerization-capable photochromic acrylic composition between two sheets of organic glass under the influence of light and / or heating.

First, a polymerization photochromic acrylic composition according to this invention is considered, and then other objects of the present invention.

According to the invention, a mixture of polymerizable compounds is used to achieve the required properties of said acrylic composition in liquid and solidified state.

In the General case, the composition consists of:

1. Oligomers with two (meth) acrylic groups with a flexible oligomeric block.

2. Oligomers with two (meth) acrylic groups with a rigid oligomeric block.

3. Photochromic organic compounds.

4. A plasticizer is an oligomer with a flexible oligomer block without one or both (meth) acrylic groups.

5. Polymerization-like solvent (monomer).

6. The initiator of thermal and / or photochemical polymerization.

Any known compound can be used as an oligomer with a flexible oligomer unit if it contains two (meth) acrylic groups linked by a divalent radical containing more than 10 ether bonds.

A typical example of an oligomer with a flexible oligomeric block is an oligomer of structure (I):

where R ¹ selected from the group -H, -F or CH ₃ ;

R ² is a divalent group:

where R ³ selected from the group-H or-CH ₃ ; n is an integer from 0 to 10;

X is a divalent organic group with an ester, carbonate or urethane group:

-YR ⁴ -Y-,

where Y is a divalent group selected from the 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 10 to 250;

R ⁵ is a divalent organic radical selected from the group:

where n is an integer from 4 to 8.

Preferred oligomers of structure (I) with a flexible oligomer are represented by compounds of formulas (1), (2) and (3):

where (1) R ¹ = CH ₃ , R ² = H, n = 0, m = 15-20 (hereinafter referred to as OUMA);

(2) R ¹ = H, R ² = CH ₃ , n = 3-5, m = 15-20;

(3) R ¹ = CH ₃ , R ² = CH ₃ , n = 3-5, m = 15-20.

Compounds (1) - (3) were synthesized by the reaction of macrodiisocyanate based on oligotetrahydrofuran-α, ω-diol with a molecular weight of about 1400 and toluene diisocyanate with ethylene glycol monomethacrylate (MEG) or with polyoxypropylene glycol monoacrylate or monomethacrylate PP (5Somethylene) respectively.

Other examples of oligomers of structure (I), in addition to the above, include polyalkylene glycol di (meth) acrylates, such as polyethylene glycol di (meth) acrylates with an average molecular weight of 300-1500, 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 perfluoroheptylethylene glycol di (meth) acrylates with an average molecular weight of 500-600.

Any known compound can be used as an oligomer with a rigid oligomeric block if it has 2 (meth) acrylic groups linked by a divalent radical containing aromatic groups.

A typical example of an oligomer with a rigid oligomeric block can be represented by structure (II):

where R ³ selected from the group -H, -F or CH ₃ ; R ^{4 is} selected from the group —H or —OH, n is an integer from 1 to 20; m = 0 or 1.

Preferred oligomers of structure (II) with a rigid oligomeric block are bisphenol A diglycidyl ether dimethacrylate (bis-GMA) and its ethoxylated and glycerated acrylic analogues of formulas (4), (5) and (6), respectively:

The polymerization compositions of this invention may include a plasticizer in addition to the aforementioned bifunctional oligomers (I) and (II). This is preferable from the point of view of achieving optimal characteristic properties, such as the density of the polymer network and, therefore, the elasticity of the network optical polymer.

These new compounds (III) are specially synthesized (see examples) to increase the elasticity of network optical polymers. Plasticizers (III) were obtained according to the method developed for the synthesis of OUM, but with the replacement of 0.33, 066 or 100 parts of telogen - MEG with an equimolecular amount of non-polymerization isopropanol (oligomers OUM-1, OUM-2 and OUP, respectively):

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

The polymerization composition of the present invention includes radically polymerizable monomers in addition to the aforementioned bifunctional oligomers (I) and (II). This is preferable from the point of view of regulating the viscosity of the composition and achieving characteristic properties, such as resistance to solvents, hardness and heat resistance of the cured product, or photochromic properties, such as staining intensity, decoloration rate and photochromic retention time.

The choice of radically polymerizable monomers is practically unlimited, and any known compounds having a radically 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.

Useful monomers include unsaturated carboxylic acids and derivatives thereof, such as methyl methacrylate, butyl methacrylate, benzyl (meth) acrylate, 2-hydroxyethyl methacrylate and hydroxypropylene glycol monomethacrylate; methylthioacrylate, benzylthioacrylate and benzylthiomethacrylate; styrene, α-chlorostyrene, α-methylstyrene, α-bromstyrene and N-vinylpyrrolidone.

In the present invention, the choice of an organic compound with photochromic properties is limited only by compatibility with the acrylic composition. Many commercially available photochromic organic compounds can be used. From the point of view of working photochromic characteristics, spiropyran, spirooxazine or naphthopyran photochromes are most preferred as a photochromic organic compound.

Examples of spiropyran compounds include 1 ', 3', 3'-trimethylspiro (2H-1-benzopyran-2,2'-indoline), 1 ', 3', 3'-trimethylspiro-8-nitro (2H-1-benzopyran- 2,2'-indoline), 1 ', 3', 3'-trimethyl-6-hydroxyspiro-8-nitro (2H-1-benzopyran-2,2'-indoline), 1 ', 3', 3'- trimethyl-8-methoxyspiro-8-nitro (2H-1-benzopyran-2,2'-indoline), 5'-chloro-1 ', 3', 3'-trimethylspiro (2H-1-benzopyran-2,2 ' -indoline), 6,8-dibromo-1 ', 3', 3'-trimethylspiro (2H-1-benzopyran-2,2'-indoline), 8-ethoxy-1 ', 3', 3 ', 4' , 7'-pentamethyltrimethylspiro (2H-1-benzopyran-2,2'-indoline), 5'-chloro-1 ', 3', 3'-trimethylspiro-6,8-dinitro (2H-1-benzopyran-2, 2'-indoline), 1,3,3-triphenylspiro [indolin-2,3 '- (3H) -naphtho (2,1-b) p Iran], 1 - (2,3,4,5,6-pentamethylbenzyl) -3,3-dimethylspiro [indolin-2,3 '- (3H) -naphtho (2,1-b) pyran], 1- ( 2-methoxy-5-nitrobenzyl) -3,3-dimethylspiro [indolin-2,3 '- (3H) -naphtho (2,1-b) pyran], 1- (2-nitrobenzyl) -3,3-dimethylspiro [indolin-2,3 '- (3H) -naphtho (2,1-b) pyran], 1- (2-naphthylmethyl) -3,3-dimethylspiro [indolin-2,3' - (3H) -naphtho ( 2,1-b) pyran] and 1,3,3-trimethyl-6'-nitrospiro [2H-1-benzopyran-2,2 '- [2H-] indole].

Examples of spirooxazine compounds include 1,3,3-trimethylspiro [indolin-2,3 '- [3H] naphtho [2,1-b] [1,4] oxazine], 5-methoxy-1,3,3-trimethylspiro [ indolino-2,3 '- [3H] naphtho [2,1-b] [1,4] oxazine], 5-chloro-1,3,3-trimethylspiro [indolino-2,3' - [3H] naphtho [ 2,1-b] [1,4] oxazine], 4,7-diethoxy-1,3,3-trimethylspiro [indolino-2,3 '- [3H] naphtho [2,1-b] [1,4 ] oxazine], 5-chloro-1-butyl-3,3-dimethylspiro [indolino-2,3 '- [3H] naphtho [2,1-b] [1,4] oxazine], 1,3,3, 5-tetraomethyl-9'-ethoxyspiro [indolino-2,3 '- [3H] naphtho [2,1-b] [1,4] oxazine], 1-benzyl-3,3-dimethylspiro [indolino-2,3 '- [3H] naphtho [2,1-b] [1,4] oxazine], 1- (4-methoxybenzyl) -3,3-dimethylspiro [indolino-2,3' - [3H] naphtho [2,1 -b] [1,4] ok sazin], 1- (2-methoxybenzyl) -3,3-dimethylspiro [indolin-2,3 '- [3H] naphtho [2,1-b] [1,4] oxazine], 1- (3,5- dimethylbenzyl) -3,3-dimethylspiro [indolino-2,3 '- [3H] naphtho [2,1-b] [1,4] oxazine], 1- (4-chlorobenzyl) -3,3-dimethylspiro [indolino -2,3 '- [3H] naphtho [2,1-b] [1,4] oxazine], 1- (4-bromobenzyl) -3,3-dimethylspiro [indolino-2,3' - [3H] naphtho [2,1-b] [1,4] oxazine], 1- (2-fluorobenzyl) -3,3-dimethylspiro [indolino-2,3 '- [3H] naphtho [2,1-b] [1, 4] oxazine], 1,3,5,6-tetramethyl-3-ethylspiro [indoline-2,3 '- [3H] pyrido [3,2-f] [1,4] benzoxazine], 1,3,3 , 5,6, -pentamethyl-3-ethylspiro [indolin-2,3 '- [3H] pyrido [3,2-f] [1,4] benzoxazine-], 6' - (2,3-dihydro- 1H-indol-1-yl -) - 1,3-dihydro-3,3-dimethyl-1-propylspiro [2H-indol-2,3 '- [3H] naphtho [2,1-b -] [1,4] oxazine], 6' - (2,3-dihydro-1H-indol-1-yl) -1 , 3-dihydro-3,3-dimethyl-1- (2-methylpropyl-spiro [2H-indol-2,3 '- [3H] naphtho [2,1-b -] [1,4] oxazine], 6 '- (2,3-dihydro-1H-indol-1-yl) spiro [2H-indol-2,3' - [3H] naphtho [2,1-b] [1,4] oxazine], 1,3 , 3-trimethyl-6- (1-piperidinyl) spiro [2H-indole-2,3 '- [3H] naphtho [2,1-b] [1,4] -oxazine], 1,3,3-trimethyl -6 '- (1-piperidinyl) -6- (trifluoromethyl) spiro [2H-indol-2,3' - [3H] naphtho [2,1-b] [1,4] -oxazine] and 1,3, 3,5,6-pentamethylspiro [2H-indole-2,3 '- [3H] -naphtho [2,1-b] [1,4] oxazine].

Examples of naphthopyran compounds include 3,3-diphenyl-3H-naphtho [2,1-b] pyran, 2,2-diphenyl-3H-naphtho [2,1-b] pyran, 3- (2-fluorophenyl) -3- (4-methoxyphenyl) -3H-naphtho [2,1-b] pyran, 3- (2-methyl-4-methoxyphenyl) -3- (4-ethoxyphenyl) -3H-naphtho [2,1-b] pyran, 3- (2-furyl) -3- (2-fluorophenyl) -3H-naphtho [2,1-b] pyran, 3- (2-thienyl) -3- (2-fluoro-4-methoxyphenyl) -3H- naphtho [2,1-b] pyran, 3- {2- (1-methylpyrrolidinyl)} - 3- (2-methyl-4-methoxyphenyl) -3H-naphtho [2,1-b] pyran, spiro (bicyclo [ 3.3.1] nonan-9,3'-3H-naphtho [2,1-b] pyran), spiro (bicyclo [3.3.1] nonan-9,2'-3H-naphtho [2,1-b] pyran ), 4- [4- [6- (4-morpholinyl) -3-phenyl-3H-naphtho [2,1-b] pyran-3-yl] phenyl] morpholine, 4- [3- (4-methoxyphenyl) -3-phenyl-3H naphtho [2,1-b] pyran-3-yl] phenyl] morpholine, 4- [3,3-bis (4-methoxyphenyl) -3H-naphtho [2,1-b] pyran-3-yl] phenyl ] morpholine, 4- [3-phenyl-3- [4- (1-piperidinyl) phenyl] -3H-naphtho [2,1-b] pyran-3-yl] phenyl] morpholine and 2,2-diphenyl-2H naphtho [2,1-b] pyran.

From the point of view of the objectives of the present invention, the most promising photochromic compounds are 1,3-dihydro-1,3,3-trimethylspiro [2H-indole-2,3 '- [3H] anthro [2,1-b] [1,4] oxazine] (SAO), 1,3-dihydro-1,3,3-trimethyl-5'-indolinocarbonylspiro [2H-indole-2,3 '- [3H] naphtho [2,1-b] [1,4] oxazine] (InSAO), 3-phenyl-3-ferroceryl-3H-anthro [2,1-b] pyran (FeChr), 3,3-bis (2,4-dimethoxyphenyl) -5-indolinocarbonyl- [3H] naphtho [2,1-b] [1,4] oxazine (NChr), 3,3-bis (4-methoxyphenyl) -3H-anthro [2,1-b] pyran (AChr), bis (phenyldiazenecarboxylic acid 2- ( phenylhydrazidato-N ² , S) - (mercury (II), diphenylthiocarbazone) (HgDTZ).

Photochromic compounds SAO, FeChr, and HgDTZ are the most representative for revealing the essence of the present invention, and most of the experiments were carried out specifically with these photochromes;

In the General case, the content of the components of the composition can vary within wide limits:

The oligomer represented by structure (I) is 20-80 mass. parts

The oligomer represented by structure (II) is 0-50 mass. parts

Photochromic organic compound - 0.01-10 mass. parts

The plasticizer represented by structure (III) is 0-40 mass. parts

Polymerization solvent (monomer) - 1-30 mass. parts

More preferred polymerization compositions of the following composition:

The oligomer represented by structure (I) is 40-60 mass. parts

The oligomer represented by structure (II) is 15-30 mass. parts

Photochromic organic compound - 0.1-1.0 mass. parts

The plasticizer represented by structure (III) is 0-40 mass. parts

Polymerization solvent (monomer) - 10-30 mass. parts

The preparation of a photochromic crosslinked product by three-dimensional free radical polymerization of the specified acrylic composition can be carried out using all known initiation methods: thermal, photochemical using light wavelengths from the ultraviolet region to ~ 550 nm, or α, β, or γ radiation, or a combination the methods listed above.

Many of the known radical polymerization initiators can be used to cure the liquid photopolymerization composition of this invention.

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'-azo-bis (4-dimethylvaleronitrile), 2,2'-azo-bis (2-methylbutyronitrile) and 1, 1'-azo-bis (cyclohexane-1-carbonitrile).

The amount of thermal polymerization initiator depends on the polymerization conditions, the type of initiator, the structure of the components and the composition of the oligomers and monomers and can vary widely. The preferred concentration of the initiator is from 0.01 to 10 mass. parts per 100 mass. parts of the total amount of all polymerization compounds. Thermal polymerization initiators can be used both separately and in 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. -phenylpropan-1-one, benzylmethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-isopropylthioxantone, bi oxide (2,6-dimethoxybenzoyl-2,4, 4-trimethylpentyl) phosphine, bi (2,4,6-trimethylbenzoyl) phenylphosphine oxide, approx Id trimetilbenzoildifenil-2,4,6-phosphine or a 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1 -butanon.

It is possible to use either one or a combination of two or more photoinitiators, as well as in combination with a thermal polymerization initiator.

In the present invention, the photochemical curing of acrylic compositions is preferably carried out using a mixture of (1: 1) diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and 2-hydroxy-2-methylpropiophenone (hereinafter referred to as FI).

The photopolymerization initiator is used in an amount of from 0.01 to 5 masses. parts per 100 mass. parts of the total number of all monomers.

The most preferred method of photopolymerization of a photochromic acrylic composition according to this invention involves the use of UV radiation in the presence of a photoinitiator, followed by heating to complete the polymerization.

For three-dimensional photopolymerization of the composition according to this invention, any known source of ultraviolet radiation 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 to one of the listed light sources is determined by the type of lamp, absorption wavelength, sensitivity of the initiator of photopolymerization and the thickness of the photochromic layer.

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

Table 1 presents the abbreviations of the most commonly used components of the compositions.

Table 1. Components of a polymerization photochromic acrylic composition. Abbreviation Structure MEG Ethylene glycol monomethacrital OUM Oligourethane methacrylate from MEG and macrodiisocyanate based on oligotetrahydrofuran-α, ω-diol and toluene diisocyanate (Synthetic example A) OUM-1 Monoisopropoxy oligourethane monomethacrylate - an OUMA analog obtained using a mixture of MEG and isopropanol in the ratio 0.33: 0.66 (Synthetic example E) OUM-2 Monoisopropoxy oligourethane monomethacrylate - an OUMA analog obtained using a mixture of MEG and isopropanol in a ratio of 0.33: 0.66 (Synthetic example F) OUM-3 Oligourethane methacrylate from Bissomer PPM5S and Macrodiisocyanate based on oligotetrahydrofuran-α, ω-diol and toluene diisocyanate (Synthetic Example D) PMO Diisopropoxy oligourethane from isopropanol and macrodiisocyanate based on oligotetrahydrofuran-α, ω-diol and toluene diisocyanate (Synthetic example G) IFUM Isophoronurethane dimethacrylate (Synthetic Example H) Tmpa Trimethylopropane triacrylate OKM-2 ™ Oligocarboanate methacrylate from diethylene glycol bischloroformate and MEG Bis-GMA Bisphenol A diglycidyl ether dimethacrylate Bis-FEA Bisphenol A Ethoxylated Diglycidyl Ether Diacrylate Bis-FGA Bisphenol A diglycidyl ether glycerolate diacrylate AMA Allyl methacrylate Bzma Benzyl methacrylate BMA Butyl methacrylate TsGMA Cyclohexyl methacrylate DDMA Dodecyl methacrylate GMA Hexyl methacrylate MMA Methyl methacrylate OMA Octyl methacrylate N-VP N-vinylpyrrolidone Sao 1,3-dihydro-1,3,3-trimethylspiro [2H-indole-2,3 '- [3H] anthro [2,1-b] [1,4] oxazine] Fcchr 3-Phenyl-3-ferroceryl-3H-anthro [2,1-b] pyran Hgdtz Bis (phenyldiazenecarbotic acid 2- (phenylhydrazidato-N ² , S) - (mercury (II), diphenylthiocarbazone) FI Photoinitiator - a mixture (1: 1) diphenyl (2,4,6-trimethylbenzoyl) phosphinokiside and 2-hydroxy-2-methylpropiophenone AIBN Azo bis isobutyronitrile PU Industrial Linear Polyurethane

The fact of the adverse effect of some vinyl components of the compositions on the photochromic properties of the materials obtained, in particular on their tintability and light fastness, as well as in some cases on the polymerization rate of the composition, has been discovered.

,

) и оптическая плотность образцов в максимуме поглощения окрашенной формы в фотостационарном состоянии (

) при облучении излучением ксеноновой газоразрядной лампы, имитирующей солнечное излучение летом в полдень. В данных экспериментах композиции содержали 0,2% масс. SAO и отверждались в присутствии 1% масс. АИБН в двух различных условиях полимеризации : 50°С, 340 мин или 80°С, 120 мин соответственно.So it was found that styrene and N-VP have a strong negative effect on the optical properties of the studied triplexes. In this regard, the influence of the structure of linear polyalkyl methacrylates obtained by thermal polymerization of acrylic monomers, the main components of the compositions, on the photochromic properties of SAO was studied. The data from these preliminary studies (preliminary examples of PP1-PP7) are presented in Tables 2 and 3: the initial absorbance of the samples at the wavelengths of unpainted and colored products (

,

) and the optical density of the samples at the absorption maximum of the colored form in the photostationary state (

) when irradiated with xenon gas discharge lamp simulating solar radiation in the summer at noon. In these experiments, the composition contained 0.2% of the mass. SAO and cured in the presence of 1% of the mass. AIBN under two different polymerization conditions: 50 ° C, 340 min or 80 ° C, 120 min, respectively.

table 2 Photochromic properties of polyalkyl methacrylates containing 0.2% of the mass. Sao Example PP1 PP2 PP3 PP4 PP5 PP6 PP7 Monomer MMA BMA GMA TsGMA ** OMA AMA DCMA 80 ° C, 120 min h * mm 2.2 2.6 1.9 2.8 1.5 - -

> 3.0 > 3.0 > 3.0 > 3.0 1.5 - -

0.49 0.26 0.26 0.25 0.12 - -

0.8 1.4 1.8 1.4 1,2 - - h * mm 0.7 0.5 - 0.7 0.8 0.7 0.8

1.0 0.7 - 2.1 1.5 1.3 1.7

0.06 0.02 - 0.21 0.14 0.07 0.13

0.75 0.1 - 0.94 0.8 0.82 0.87 50 ° C, 340 min h * mm 2.7 2.6 2.5 2.2 0.4 2.3 -

> 3.0 ~ 3.0 > 3.0 > 3.0 ~ 3.0 ~ 3.0 -

0.37 0.1 0.16 0.17 0.16 0.7 -

0.9 1.6 1.95 1.1 1.6 1.6 - * Sample thickness ** Cure time 545 min

The results obtained show that alkyl methacrylates polymerize faster and to deeper degrees of conversion of double bonds in the absence of photochrome. So, in the presence of SAO photochrome, the polymerization rate is significantly reduced, but the polymerization products practically do not contain defects caused by shrinkage and stress development.

Nevertheless, the data presented show that under optimal conditions (PP2-PP4) the optical characteristics of photochrome in acrylic matrices are quite comparable with those achieved in an inert solvent, for example toluene.

Table 3 shows the data on the influence of the polymerization conditions of acrylic compositions containing SAO, FeChr or HgDTZ photochromes on the photochromic properties of a crosslinked polymer (examples PP8 - PP23). The composition was used: 60% OUMA, 20% BMA and 20% OMA. 1% AIBN (composition A-1) was introduced as an initiator for thermopolymerization, and 1% PI (composition A-2) for photochemical polymerization. Due to its low solubility in acrylates, it is necessary to use N-VP in compositions with HgDTZ, and we studied the composition of 60% OUM, 20% N-VP, and 20% OMA in the presence of 1% AIBN or PI for thermal and photoprocesses (composition B-1 and B-2, respectively).

The measured parameters were the appearance of the forming triplex, its color, the degree of completion of curing by organoleptic properties, adhesion to a PC or a protective coating on a PC, and also the physical parameter ΔD is the change in the optical density of the sample at the absorption maximum of the colored form when irradiated with Xe a lamp that simulates solar radiation in the summer at noon.

Table 3 Properties of reticulated photochromic optical polymers Example Composition Photochrome,% of the mass. Curing conditions, h *, mm ΔD Sample quality PP8 A-1 SAO, 0.1 70 °, 220 min, 1 mm 1.5 Satisfactory PP9 A-1 SAO, 0.1 70 °, 220 min, 2 mm 1.8 Satisfactory PP10 A-1 FeChr, 0.1 60 °, 200 min 2 mm 0.26 Incomplete polymerization PP11 A-2 FeChr, 0.1 hν *, 4.5 min, 1 mm 0.18 Good PP12 A-2 FeChr, 0.2 hν, 2 min, 1 mm 0.34 Good PP13 A-1 FeChr, 0.2 70 °, 240 min, 1 mm 0.32 Bad PP14 A-2 FeChr, 0.1 hν, 2 min, 1 mm 0.23 Good PP15 A-2 FeChr, 0.1 hν, 2 min, 2 mm 0.26 Good PP16 IN 1 HgDTZ, 0.1 60 °, 200 min, 1 mm 1.2 Incomplete polymerization PP17 IN 1 HgDTZ, 0.1 60 °, 200 min, 2 mm 1.5 Incomplete polymerization PP18 IN 2 HgDTZ, 0.1 hν, 4.5 min, 1 mm - No photochromism PP19 IN 2 HgDTZ, 0.1 hν, 4.5 min, 2 mm 1.0 Good PP20 IN 2 HgDTZ, 0.2 hν, 4 min, 1 mm 1.1 Good PP21 IN 2 HgDTZ, 0.2 hν, 9 min, 2 mm 1.2 Bad PP22 IN 1 HgDTZ, 0.2 70 °, 240 min, 1 mm 1.3 Good PP23 IN 1 HgDTZ, 0.2 70 °, 240 min, 2 mm 1.0 Satisfactory PP24 PU Sao 1.6 Comparative example PP25 PU Fechr 0.3 Comparative example PP26 PU Transgray ™ 1.2 Comparative example * Irradiation with a high pressure mercury lamp, 1000 watts.

Obviously, the free radicals involved in the polymerization of oligomers interact with photochromic compounds, reducing the photochromic properties of the network polymer. To reduce the concentration of radicals initiating polymerization, the slow process initiated by material initiators at moderate temperatures was optimal. The thermally initiated polymerization of monomer-oligomeric mixtures eliminates the undesirable effect of free radicals and obtain slightly colored samples of satisfactory quality with a colorability of AD> 1.0 (Table 3). As the thickness of the sample increases, the colorability increases, but not in proportion to the increase in thickness.

For comparison, triplexes based on linear polyurethane (PU) were obtained with the introduction of photochrome, including commercial Transgray ™, through a solution in a low boiling solvent, i.e. without the participation of the polymerization process. The colorability of such triplexes is comparable with the values of this parameter in SAO-12 and FeChr composites with reactive compounds under the same irradiation conditions (Table 3).

The most successful initiator of thermal polymerization is AIBN, for which the decay rate constant at 50-80 ° C is (3-12) × 10 ^-6 sec ¹ .

In the process of this study, it was found that at elevated temperatures, acrylic compositions destroy the surface of organic glasses due to the diffusion of monomers from the liquid composition into the glass surface. To protect the surface of organic glasses from swelling in an environment of acrylic monomers, leading to clouding of triplexes, it is proposed to apply a protective coating to organic glasses in a fast photochemical process. To create a coating, a composition of isophoronurethane dimethacrylate (IFUM) and trimethylolpropane triacrylate (TMPA) in the presence of a photoinitiator was developed. The result is a transparent, colorless, hard, shiny protective coating with good adhesion to organic glass and resistance to mixtures of acrylic monomers at elevated temperatures:

The use of plasticizers of structure III makes it possible to change the density of the chemical network and, therefore, the elasticity of the crosslinked optical polymer. It can be seen that the partial replacement of the OUMA by OUM-1, OUM-2 or OUP (examples PP27 - PP32) leads to a slight increase in the tintability of the cured products (Table 4). An increase in the density of the network leads to lower values of the optical density of the samples at the maximum absorption of the colored form at the same content of the photochromic compound.

Table 4 Photochromic properties of plasticized samples of network photochromic optical polymers containing 0.1% of the mass. SAO (1% AIBN, 80 ° C, 30 min, sample thickness 0.8 mm) Example Oligomer

PP27 OUM 1.19 0.09 1.26 PP28 OUM-1 1.25 0.106 1.30 PP29 OUM-2 1.46 0.11 1.35 PP30 PMO 1.41 0.13 0.91 PP31 OUM + 25% OUP 1.21 0.11 1.22 PP32 OUM + 50% OUP 1.25 0.11 1.23 PP33 PU 1.04 0.12 1.08 Comparative

Any known transparent sheet polymeric materials can be used as the outer layers of triplex. For this invention, it is preferable to use sheets of polycarbonate or polymethyl methacrylate with a thickness of 0.1 to 2 mm, preferably 0.5-2.0 mm thick.

The manufacture of photochromic triplexes based on organic glasses according to this invention is carried out using the process below. A photochromic organic compound is added to a mixture of oligomers and monomers in a concentration of 0.2 to 5% by mass. from the total load of the liquid acrylic composition. The mixture is stirred for 5-90 minutes until a clear solution is achieved. Then the initiator is added in a given concentration and the resulting photochromic acrylic composition is mixed for 5-10 minutes. Gaskets of a given thickness are placed along the perimeter of the surface of a sheet of organic glass (with or without a protective coating applied in advance), a second sheet of organic glass is installed on top of the strip and the assembled form is fixed with clamps. The required amount of polymerization-capable photochromic acrylic composition is poured into the mold, and the "raw" triplex undergoes three-dimensional polymerization when heated or irradiated with light. As a rule, the obtained triplex is additionally subjected to heat treatment above the glass transition temperature of the cross-linked polymer.

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

Examples

The names and accepted abbreviations used in the work of the compounds are given above in Table 1.

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

500 g (0.5 mol) of oligotetrahydrofuran-α, ω-diol of diisocyanate (M _n ≈1000), 140.8 g (1.1 mol) of ethylene glycol monomethacrylate (MEG) and 0.5 g of tin dilaurate are stirred at room temperature for 12 hours until the isocyanate groups are completely consumed according to 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 = 1.5095.

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

Oligourethane methacrylates (OUMA) of structures (2) and (3) were 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 mole of telogen - “Bisomer ™” PPA5S (423.6 g) or "Bisomer ™" PPM5S (398.2 g), respectively.

Synthetic examples of E-G. Synthesis of plasticizers OUM-1, OUM-2 and OUP structures (4) - (6).

The plasticizers OUM-1, OUM-2 and OUP were obtained from 500 g (0.5 mol) of oligotetrahydrofuran-α, ω-diol diisocyanate according to the procedure of Synthetic Example A using instead of MEG 1.1 mol of a mixture of telogens - MEG and / or isopropanol:

Structure (4) of 0.73 and 0.37 mol of MEG and isopropanol, respectively.

Structure (5) 0.37 and 0.73 mol of MEG and isopropanol, respectively.

Structure (6) 1.1 moles of isopropanol.

Synthetic Example N. Synthesis of isophoronurethane methacrylate.

Isophoronurethane methacrylate was obtained by the reaction of isophorondiisocyanate with MEG according to the procedure of Synthetic Example A.

Preliminary Example 1.

A mixture of 10 g MMA, 0.1 g AIBN and 0.02 g SAO was thoroughly mixed until a homogeneous solution was obtained. A gasket - a polytetrafluoroethylene ring 0.7, 2.2 or 2.7 mm thick was placed on the surface of silicate glass and the obtained forms were filled with the composition. The first two forms were heated at 80 ° C for 120 minutes, and the third at 50 ° C for 340 minutes. The optical properties of the obtained linear polymer are given in Table 2.

Preliminary examples 2-7.

Similarly to Preliminary Example 1, linear polymers BMA, GMA, TsGMA, OMA, AMA, DDMA were obtained, respectively. The optical properties of the obtained linear polymers are given in Table 2.

Preliminary Example 8.

60% of the mass. Oligourethane methacrylate OUMA, 20% BMA, 20% OMA and 1% AIBN (mixture A) and 0.1% photochromic compound SAO were mixed in the same way as in Example 1. The mixture was heated at 70 ° C for 220 min and a network optical polymer was obtained. The optical properties of the polymer are given in Table 3.

Preliminary Examples 9-23.

Similar to Preliminary Example 8, network optical polymers were obtained by thermal or photochemical polymerization of mixtures A-1, A-2, B-1 and B-2 containing the photochromic compound SAO, FeChr and Hg-DTZ. The optical properties of the polymers are shown in Table 3.

Preliminary Examples 24-26.

0.1% of the mass. The photochromic compound SAO, FeChr or Transgray ™ (commercial product) was added to a 20% solution of linear polyurethane in dichloromethane. After complete dissolution, the mixture was applied to the surface of silicate glass, and after removal of the solvent by the usual method, films were obtained whose properties are shown in Table 3.

Preliminary Example 27.

A 7 mm thick gasket was placed along the surface contour of silicate glass and the obtained form was filled with a mixture of 5 g OUMA, 0.1% of the mass. SAO and 1% AIBN. After heating at 80 ° C for 30 min, a network optical polymer was obtained, the properties of which are shown in Table 4.

Preliminary Examples 28-32.

Similarly to Preliminary example 27, a network optical polymer was obtained by thermal polymerization of the oligomers listed in Table 4. The table also shows the optical properties of the obtained polymers.

Preliminary Example 33.

By a method similar to that in Preliminary Examples 24-26, films of linear polyurethane were obtained. The optical properties of the obtained polymer are given in Table 4.

Example 1. Obtaining photochromic polycarbonate triplex.

40.0% of the mass. OUMA, 30.0% IFUA, 9.5% BMA, 19.5% TSHMA, and 0.1% SAO were loaded into a dark glass vessel. The mixture was stirred with a mechanical stirrer for 30 minutes until a clear solution was obtained. Then 1.0% AIBN was added and the composition was mixed for another 5-10 minutes. A gasket 1.0 mm thick from (tape, nylon line, fiber or organic fiber tow) is placed around the perimeter of the polycarbonate sheet without a protective coating and ~ 5 g of the prepared composition is poured into the resulting form. After spreading the composition, the mold is covered with a second polycarbonate sheet and the assembly is fixed with clamps (clamps). The assembly is heated at 50 ° for 290 minutes and then at 60 ° for 130 minutes. After disassembling the form, a photochromic polycarbonate triplex is obtained, the properties of which are shown in Table 5.

Table 5. The composition, conditions for three-dimensional polymerization and the properties of photochromic polycarbonate triplexes containing SAO-12 photochrome. Example The composition,% Cure mode ΔD Sample quality 0.1% SAO-12 one OUM, 40.0 50 °, 290 min + 60 °, 130 min 1.2 Defective IFUM, 30.0 Transparent BMA, 9.5 TsGMA, 19.5 AIBN, 1.0 2 OUM, 40.0 50 °, 290 min + 60 °, 130 min 1.2 Defective IFUM, 30.0 Transparent BMA, 9.5 Pink TsGMA, 19.5 AIBN, 1.0 3 OUMA, 30.0 50 °, 400 min 1.2 Light pink bis-pEA, 30.0 Moderately defective BMA, 19.5 TsGMA, 19.5 Polymerization not completed AIBN, 1.0 four OUM, 40.0 65 °, 230 min 1.4 Without defects. IFUM, 30.0 Between silicate glasses. BMA, 9.5 TsGMA, 19.5 AIBN, 1.0 5 OUM, 35.0 100 °, 35 min 0.80 Defective Bis-GMA, 35.0 BMA, 14.5 TsGMA, 14.5 AIBN, 1.0 6 OUM, 35.0 90 °, 45 min 0.83 Virtually No Defects Bis-GMA, 35.0 BMA, 14.5 TsGMA, 14.5 AIBN, 1.0 7 OUM, 35.0 85 °, 45 min 0.88 Virtually No Defects Bis-GMA, 35.0 BMA, 14.5 TsGMA, 14.5 AIBN, 1.0 8 OUM, 35.0 85 °, 35 min 0.68 Polymerization not completed Bis-GMA, 35.0 BMA, 14.5 TsGMA, 14.5 AIBN, 1.0 9 OUM, 69.0 100 °, 30 min 1.25 Virtually No Defects BMA, 20.0 OMA, 10.0 Transparent, colorless AIBN, 1.0 10 OUM, 69.0 90 °, 45 min 1.1 Defective BMA, 20.0 Transparent OMA, 10.0 Gray AIBN, 1.0 eleven OUM, 69.0 110 °, 30 min 0.77 Matt BMA, 20.0 OMA, 10.0 AIBN, 1.0 0.2% SAO-12 12 OUMA, 30.0 100 °, 45 min 1.45 Virtually No Defects Bis-FEA, 30.0 BMA, 19.5 Transparent TsGMA, 19.5 Pink AIBN, 1.0 13 OUMA, 30.0 90 °, 30 min 2.2 Without defects Bis-FEA, 30.0 Transparent BMA, 19.5 Purple pink TsGMA, 19.5 AIBN, 1.0 fourteen PU Comparative 1,6

Examples 2 to 28. Obtaining polycarbonate photochromic triplexes.

By the methodology described in Example 1, photochromic polycarbonate triplexes were obtained from compositions whose compositions and conditions for the formation of triplex are shown in Tables 6-7. The same tables show the properties of the obtained triplexes.

Table 6 The composition, the conditions of three-dimensional polymerization and the properties of photochromic polycarbonate triplexes containing 0.2% of the mass. photochromic FeChr Example The composition,% Cure mode AD Sample quality fifteen OUMA, 60.0 DRT-1000 0.26-0.32 Transparent BMA, 19.5 2 minutes Without defects TsGMA, 19.5 AIBN, 1.0 FI 1.0 16 OUMA, 60.0 65 °, 240 min 0.29 Defective BMA, 19.5 TsGMA, 19.5 AIBN, 1.0 17 * OUM, 40.0 65 °, 230 min 0.20 Transparent IFUM, 30 Without defects BMA, 9.5 TsGMA, 19.5 AIBN, 1.0 eighteen OUM, 40.0 50 °, 290 minutes 0.26 Transparent IFUM, 30.0 + Defective BMA, 9.5 60 °, 130 min TsGMA, 19.5 AIBN, 1.0 19 OUMA, 30.0 100 °, 45 min 0.2 Transparent Bis-FEA, 30.0 Almost BMA, 19.5 without defects TsGMA, 19.5 AIBN, 1.0 twenty OUM, 40.0 85 °, 15 min 0.26 Transparent Bis-GMA, 30.0 + Defective BMA, 15.0 60 °, 45 min Incomplete TsGMA, 15.0 curing AIBN, 1.0 21 OUM, 40.0 95 °, 30 min 0.27 Transparent Bis-GMA, 30.0 Defective BMA, 15.0 Incomplete TsGMA, 15.0 curing AIBN, 1.0 22 OUM, 40.0 85 °, 30 min 0.21 Transparent Bis-GMA, 30.0 Slow Without defects* BMA, 15.0 cooling down TsGMA, 15.0 AIBN, 1.0 23 ** OUM, 40.0 85 °, 30 min 0.3 Transparent Bis-GMA, 30.0 Slow Without defects BMA, 15.0 cooling down TsGMA, 15.0 AIBN, 1.0 24 Polyurethane
Comparative 0.27 * Between silicate glasses with a protective coating. Tumble protection from glass. ** Between silicate glasses without a protective coating.

Table 7 The composition, the conditions of three-dimensional polymerization and the properties of photochromic polycarbonate triplexes containing 0.2% HgDTZN photochrome (layer thickness 1 mm) Example The composition,% Cure mode ΔD Sample quality 25 OUM, 60 65 °, 240 min 1.0 Transparent OMA, 19.5 With bubbles N-VP 19.5 AIBN, 1.0 26 OUM, 60 70 °, 240 min 1.8 Transparent OMA, 19.5 With bubbles N-VP 19.5 AIBN, 1.0 27 OUM, 40 50 °, 290 minutes 2.2 Transparent IFUM, 30 + Defective OMA, 19.5 60 °, 130 min Sticky layer N-VP 9.5 Strong adhesion AIBN, 1 to the substrate 28 OUM, 40 80 °, 30 min 1.88 Transparent IFUM, 30 Slow Without defects OMA, 19.5 cooling N-VP 9.5 Thickness AIBN, 1 2 mm layer 29th PU 2.5 Photochrome 4050 Comparative λ _max = 580 nm

Examples 30-34 (Table 8) show the optimal composition of the compositions, the conditions of three-dimensional polymerization in terms of the properties of photochromic polycarbonate triplexes. In the case of using HgDTZN as the photochromic compound, it turned out to be preferable to administer an equimolar amount of the known synergistic tinuvin.

Table 8 Characteristics of samples with an optimal combination of quality and photochromic properties of polycarbonate triplexes. Example Photochrome% The composition,% Cure conditions Photo stability, hours Sample quality thirty FeChr, IFUM, 80 °, 30 min 80 Without defects 0.1 29.8 Transparent OUM-2, 31.2 BMA, 19.5 TsGMA, 19.5 ABN, 1.0 31 FeChr, 0.1 IFUM, 26.4 DRT-1000, 4 twenty Transparent OUM-2, 32.6 min BMA, 20.0 TsGMA, 20.0 FI 1.0 32 SAO, 0.1 IFUM, 29.9 80 °, 30 min > 100 Without defects OUM-2, 29.7 Transparent BMA, 20.2 TsGMA, 20,2 ABN, 1.0 33 HgDTZN, 0.1 IFUM, 29.6 80 °, 30 min 80 Transparent Lighter Tinuvin OUM-2, 30.1 source 0.1 BMA, 20.4 N-VP 20.4 ABN, 1.0 34 HgDTZN, 0.1 IFUM, 26.7 DRT-1000, 8 40 Without defects Tinuvin OUM-2, min Transparent, 0.1 28.6 darker BMA, 19.0 source TsGMA, 19.0 N-VP 5.7 FI 1.1

Examples 35-42. Obtaining polymethylmethacrylate photochromic triplexes.

By the methodology described in Example 1, photochromic polymethylmethacrylate triplexes were obtained from compositions whose compositions and conditions for the formation of triplex are shown in Table 9. This table also shows the properties of the obtained triplexes.

Table 9. Characteristics of samples with an optimal combination of quality and photochromic properties of polymethylmethacrylate triplexes. Example Photochrome,% The composition,% Cure conditions Photo stability, hours Sample quality 35 FeChr, MILF. 29.8 80 °, 30 min 90 Without defects 0.1 OUM, 29.8 Transparent BMA, 19.6 Green TsGMA, 19.6 AIBN, 1.1 36 FeChr, OUM, 59.2 70 °, 45 min 80 Without defects 0.1 BMA, 19.7 Transparent OMA, 20.0 AIBN, 1.0 37 FeChr, OUM, 59.2 DRT-1000, 70 Without defects 0.1 OMA, 19.8 1 min Transparent BMA, 19.8 FI 1.1 38 FeChr, OUM, 59.1 DRT-1000, 90 Transparent 0.1 OMA, 19.8 4 min Lighter BMA, 19.8 source FI, 1.2 39 SAO, MILF. 29.8 80 °, 30 min > 100 Without defects 0.1 OUM, 29.8 Transparent, BMA, 19.6 Bluish TsGMA, 19.6 AIBN, 1.1 40 SAO, OUM, 59.5 DRT-1000, 60 Without defects 0.1 OMA, 19.5 1 min Transparent BMA, 19.5 Colorless FI 1.1 41 SAO, OUM, 59.5 DRT-1000, > 100 Without defects 0.1 OMA, 19.5 1 min Transparent BMA, 19.5 80 °, 30 min FI 0.6 AIBN, 0.6 42 SAO, OUM, 59.5 DRT-1000, 90 Without defects 0.1 OMA, 19.5 1 min Transparent BMA, 19.5 80 °, 30 min FI 0.7 AIBN, 0.5

The above results, especially the data of Tables 8 and 9, show that the use of a polymerization composition according to this invention allows to obtain photochromic triplexes based on organic glasses with excellent photochromic properties, as well as excellent optical properties such as colorlessness and transparency. In addition, the resulting network polymer is characterized by high elasticity and toughness, which makes it very promising for use as an inner layer of various triplexes, including those based on silicate glasses, or coatings on various substrates.

Claims (10)

1. A photochromic triplex containing two sheets of organic glass and a layer of photochromic network optical polymer placed between them, obtained by radical polymerization by photochemical or thermal initiation of an acrylic composition comprising an oligomer with two (meth) acrylic groups having a flexible oligomer unit, an oligomer with two ( meth) by acrylic groups having a rigid oligomeric block, a polymerization solvent monomer, a photochromic organic compound, a polymerization initiator. 2. Photochromic triplex according to claim 1, characterized in that the organic glasses are selected from the group consisting of polymethyl methacrylate and polycarbonate. 3. Photochromic triplex according to claim 1, characterized in that the sheet of organic glass at least on one side has a protective coating obtained by photopolymerization of acrylic oligomers. 4. Photochromic triplex according to claim 1, characterized in that the oligomer with two (meth) acrylic groups having a flexible oligomeric block contains two (meth) acrylic groups linked by a divalent radical containing more than 10 ether bonds. 5. The photochromic triplex according to claim 1, characterized in that the oligomer with two (meth) acrylic groups having a rigid oligomer block contains two (meth) acrylic groups linked by a divalent radical to aromatic groups. 6. Photochromic triplex according to claim 1, characterized in that the photochromic organic compound is selected from the group of spiropyran, spirooxazine or naphthopyran photochromic compounds. 7. Photochromic triplex according to claim 1, characterized in that the acrylic composition comprises a plasticizer selected from the group consisting of monoisopropoxy oligourethane monomethacrylate and diisoproxy oligourethane. 8. A method of manufacturing a photochromic triplex, comprising preparing a photochromic acrylic composition by mixing liquid oligomers with two (meth) acrylic groups having a flexible oligomeric block and a rigid oligomeric block, and a photochromic organic compound and the subsequent introduction of the polymerization initiator, making the mold by placing a strip of a given thickness along the perimeter of a sheet of organic glass, installing a second sheet of organic glass over the gasket and fixing the assembled form with clamps, filling collected in the form required amount of acrylic photochromic compositions and photochromic dimensional radical polymerization of acrylic composition upon thermal or photochemical initiation. 9. The method according to claim 8, characterized in that the manufactured triplex is subjected to additional heat treatment at a temperature above the glass transition temperature of the photochromic network optical polymer. 10. The method according to claim 8, characterized in that a protective coating is preliminarily applied to the surface of the sheet of organic glass by photopolymerization of a composition consisting of isophorone urethane dimethacrylate and trimethylol propane triacrylate.