Gold-containing polymerisable acrylic composition, spatial-mesh polymer material for recording information and production method thereof

FIELD: chemistry.

SUBSTANCE: composition consists of 20-80 pts.wt bifunctional acrylic oligomer, (meth)acrylic groups in which are bound by a divalent organic group with an ester, carbonate or urethane group, 20-80 pts.wt acrylic monomer selected from a alkyl(meth)acrylates or oxyalkyl(meth)acrylates, where the alkyl is a lower alkyl; 5-25 pts.wt gold salt selected from a group of inorganic salts of gold which are soluble in said acrylic monomer; 0.1-3 pts.wt photoinitiator. Also disclosed is a spatial-mesh polymer material containing dissolved gold in zero valence. Under external thermal and/or photo action, said material, which is a colourless and transparent glass-like material with not less than 90% optical transmission in the visible region, is cable of generating a plasma resonance band in the visible region of the formed gold nanoparticles - gives a response point in the 500-640 nm range. the material is obtained through photo-exposure of the said gold-containing polymerisable acrylic composition.

EFFECT: material is a recoding medium for optical recording of information and is characterised by extremely high sensitivity.

7 cl, 6 dwg, 2 tbl, 28 ex

 

The technical field to which the invention relates.

The present invention relates to photopolymerization compositions containing capable fotovosstanovlenie Sol gold, gold(0)-containing spatial-mesh polymer material (recording medium) based on them and the way to obtain this material. More specifically the invention relates to polimerizacionnye acrylic composition with dissolved salt of gold, which when pathobiochemie in the parallel processes of photopolymerization of acrylates and photovoltaikanlage gold salts forms a spatial-mesh polymer material containing dissolved gold in the zero valence, in which during subsequent thermal and/or fotomodelli geniriruetsya band plasma resonance in the visible region of the spectrum formed gold nanoparticles.

Spatial-mesh polymer material containing dissolved gold in the zero valence, can be used in all applications of the optical information recording based on secondarywinding processes in the recording environment.

The level of technology

The processes of recording information, the portable optical radiation carried out on the optical storage media physical bodies used to save the changes in them or on the surface of the optical information. These processes are based on secondarywinding processes in the recording environment, which lead to the change of state or form of media.

For the optical information recording you can use the change of any physico-chemical properties of the recording medium (electronic States, atomic structure, magnetization, etc.), but mostly use the change of two parameters: the complex refractive index ofand the optical path length l-lGn (lG- geometric path, n is the refractive index of the medium, χ characterizes the absorption). Changing the values of Δχ,, Δl under the action of optical radiation, respectively, the amplitude, phase and relief-phase entry. [Schwartz K. Physics of optical recording in dielectrics and semiconductors. Riga, 1986.]

There are several classes of optical recording media: a silver halide photochromic, electro-optical, magneto-optical, and various semiconductor is amorphous, organic, molecular. Most similar to the subject matter of the present invention are photochromic environment, especially those in which the photochromic compound is distributed in the polymer matrix. Because the recording density optical memory depends on the size of the light spot that is limited by the wavelength of light of C is the wave diffraction light, currently, this characteristic of the optical memory is already approaching its physical limit. One solution to this problem is to extend the scope of registration from the two-dimensional plane to three-dimensional space, which can be implemented in photochromic recording media. Three-dimensional registration requires the recording media, allowing for multi-layer recording, and an optical system to focus the light beam at any given point on the media capacity. Known nonlinear medium for three-dimensional registration on the basis of photochromic polymers using laser scanning confocal microscope [application U.S. 20060263541]. Such environment is proposed on the basis of polymers containing fluorescent dye [Takuo Tanaka, et. all. Optics Communications. V.212. Issues 1-3. Pages 45-50].

The above technical solutions are analogues of the present invention only by way of application records information. Close analogs and prototypes of the present invention does not exist, because we offer recording medium of the three-dimensional net-like polymer containing gold nanoparticles in the zero valence, never before used for optical recording of information.

Nanosized particles of gold are the absorption band in the visible region, due to the very local generation is about on the surface plasma resonance [Maier S. "Plasmonics: Fundamentals and Applications". 2007. Springer]. It is known [L.A. Smirnova and other Reports of the Russian Academy of Sciences. 2005. T. No. 6. S]that the plasma resonance of gold nanoparticles can be generated in the matrix of the linear polymer, such as polymethylmethacrylate, by photovoltaikanlage gold salts, distributed in the polymeric matrix. When heated obtained or otherwise of the composite particles are formed of gold the size of 20-50 nm, giving the band a plasma resonance in the region of 500-600 nm [U.S. patent 7175877]. The main use of this property of gold nanoparticles is the creation of sensors for the detection of DNA or proteins to change the local refractive index due to adsorption of the analyzed molecules on the metal surface [Englebienne P. et. al. Spectroscopy. 2003. V.17. PP.255-273] and IR-reflective coatings for lenses for different purposes [U.S. patent 7438411].

Disclosure of inventions

As a result of extensive experimental studies of the applicants were able to detect non-trivial fact, namely, that the salt of gold dissolved in polimerizacionnye the acrylate, the irradiation of the composition in the parallel running of the reactions of the photopolymerization of acrylates and photovoltaikanlage gold leads to a transparent colorless material containing dissolved Au0. In the literature and patent sources are not barouni information about how to obtain spatial-mesh polymer matrices with dissolved gold in the zero valence.

The resulting matrix may be a recording medium for optical information recording, because subsequent external influence - heating and/or irradiation - initiated the process of agglomeration of the gold particles and the point of application of the external effects generated by the plasma resonance band of gold nanoparticles in the visible region of the spectrum (500-600 nm).

The basic principle advantage of developed recording medium is extremely high sensitivity. The effective capture cross section of photon nanoparticles by 4-5 orders of magnitude greater than that of conventional dyes and the more photochromic compounds. For example, gold nanoparticles with a diameter of ~40 nm have calculated the absorption cross section 2.93·10-15m2that corresponds to the molar extinction coefficient 7.66·109M-1cm-1at the wavelength of plasma resonance 528 nm. This value is 5 orders of magnitude greater than that of the dye endocrinologi green (F=1.08 104M-1cm-1at 778 nm) [application U.S. 20080004364].

The other principal advantage of developed recording medium is the possibility of directional changes the position of the maximum absorption band of the plasma resonance within 520-640 nm due to changes in dielectric properties of the acrylic matrix (selection of original acrylic composition and).

An important advantage of the proposed technical solution is the ability to use all the advantages of oligomeric processing technology of polymeric materials in glass, films, coatings, products of arbitrary shape, since the recording medium is formed from a source of liquid acrylic composition.

For the technical solution to the problem of creating a polymer matrix with the dissolved gold in the zero valence main task is to develop a gold polimerizacionnye acrylic composition, which, upon completion of the processes photovoltaikanlage gold salts and photopolymerization of acrylic components forms a transparent and colorless spatial-mesh gold-containing polymer. In other words, the composition of gold-bearing polimerizacionnye acrylic composition should ensure the separation time photoreactive (recovery of salts and polymerization of acrylates) and sintering process Au0in nanoparticles, generating a plasma resonance.

An important task is to create a recording environment is the selection of the dielectric properties of the polymer matrix to guide the process of agglomeration of atoms Au0on the formation of nanoparticles, generating a narrow and intense band of the plasma resonance in the specified range.

Jugozapada, the decision of which is necessary for the implementation of this technical solution is the selection of the composition polimerizacionnye acrylic composition, ensuring the achievement of high salt concentrations gold without breaking homogenate system.

Was also necessary to solve the task of choosing the conditions photoreactive - recovery of gold salts and polymerization of acrylates, because it was found that these processes have a negative impact on each other.

Finally, you may want to practice the conditions for local (on the surface or in the volume of the sample) generating a plasma resonance band of the gold nanoparticles in three-dimensional polymeric matrix, since the agglomeration of the particles Au0is, apparently, a thermal process, and changing the shape of the nanoparticles by photo process.

The objectives are achieved, we offer:

- gold polimerizacionnye acrylic composition for the manufacture of polymeric recording medium for optical recording of information, consisting of:

(1) 20-80 wt. parts of a bifunctional acrylic oligomer;

(2) 20-80 wt. parts acrylic monomer;

(3) 5-25 wt. parts gold salts;

(4) 0.1-3 wt. part of photoinitiator.

Bifunctional acrylic oligomers can have the following structure:

where R1=-H, -F or CH3;

R2is a divalent group of the formula:

where R3=-N or CH3; n is an integer from 0 to 10;

X is a divalent organic group with ether, carbonate or urethane group of the formula: -Y-R4-Y-,

where Y is a bivalent group-O-,-CO-, -COO-, -CONH-R5-or-R5NHCO-,

R4is a divalent organic group of the formula:

-(CH2)l-where l=2-25, or

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

R5is a divalent organic group of the formula:

-(CH2)n-,,

where n=2-8.

The acrylic monomers can have the following structure:

,

where R1=-H, -F or CH3;

R7= alkyl2-C20, -(CH2)nIs HE, where n=2-8,

where R1and R2above.

As gold salts may be any capable of fotovosstanovlenie salt of gold.

- spatial-mesh polymer material containing dissolved gold in the zero valence, which is a product of the irradiation of the specified declared gold p is liberationsans acrylic composition, capable with external heat and/or fotomodelli to the generation of the plasma resonance band in the visible region of the spectrum formed gold nanoparticles.

The proposed spatial-mesh polymer material is a colorless and transparent glass-like material with an optical transmittance in the visible spectral range not lower than 90%.

The proposed spatial-mesh polymer material can serve as a recording medium for optical information recording, because the local impact, for example by a laser beam, gives the point-response in the field 500-640 nm.

- method of obtaining spatial-mesh polymer material containing dissolved gold in the zero valence, comprising the following stages:

(1) preparation of a solution of salt of gold acrylic monomer;

(2) preparation of the claimed gold polimerizacionnye acrylic composition by mixing a solution of salt of gold acrylic monomer with a bifunctional acrylic oligomer and photoinitiator;

(3) pathobiochemie composition in the form of quartz or silicate glass.

The proposed composition, spatial-mesh polymer material and method for producing it are unparalleled.

Brief description of drawings

Figure 1 shows absorption spectra of a solution of HAuCl4 in the acrylic composition of example 1 in the irradiation process.

(a) the Expenditure of HAuCl4. Curves 1-12 correspond 0-5 .3 min exposure.

(b) Growth bands plasma resonance. Curves 1 and 14 through 23 and 113 min after the start of exposure.

Figure 2 shows the kinetics of accumulation strips plasma resonance when irradiated gold acrylic compositions. Curves 1-8 - the compositions of examples 11, 12, 3, 4, 5, 6, 8 and 1, respectively.

Figure 3 shows the electronic absorption spectra of films of gold-spatial-mesh polymer after completion of the photochemical and thermal processes. The numbers on the spectra correspond to the numbers of embodiments of the invention.

Figure 4 illustrates the effect of the structure of the oligomer and conditions of photoreactive on the process of generating the plasma resonance band. The numbers on the spectra correspond to the numbers of embodiments of the invention.

Figure 5 is given a photograph of scanning electron micrographs of sections of sample according to example 13 with nanosized particles of gold - product photovoltaikanlage HAuCl4in the environment of the acrylic composition of example 1.

6 illustrates the use of the inventive spatial gold-mesh polymer according to example 13 as a recording environment:

figure 6 and shows the image obtained by irradiation of the claimed plank is through the metal lattice hole diameter of 200 microns, and figure 6,b is an arbitrary image on the surface of a colorless transparent film by means of a point of the heating element with a temperature of 100-130°C.

The implementation of the invention

The creation of the present invention required a large amount of experimental research. First, it was necessary to solve the problem of realization of two parallel photoreactive - recovery of gold salts and polymerization of acrylates, because it is very likely negative impact of salt or organic products recovery of free radical polymerization.

Further demanded an answer key question is whether it is feasible to generate plasma resonance band of gold nanoparticles in the spatial-mesh polymer matrix, because the grid limits the various diffusion processes, including the agglomeration of the gold particles.

If a positive result is the following problem: is there a possibility to obtain a stable solution Au0in the polymeric matrix, since the possibility of using gold matrix as a recording medium is determined by this property.

It was necessary also to determine the influence of the composition of the acrylic composition and structure of its components on the efficiency of the implementation process of the plasma resonance position, extinction and bandwidth in the visible region of the spectrum.

Finally, it was necessary to explore the possibility of recording information on the surface and in the volume of spatial-mesh polymer material containing dissolved gold in the zero valence.

The carried out researches have allowed to solve the problems listed above.

It was found that any radically polymerizable compound may be used as bifunctional acrylic oligomer, if it contains two (meth)acrylic groups associated divalent radical.

A typical example of a bifunctional acrylic oligomer is an oligomer of structure (I):

where R1=-H, -F or CH3;

R2is a divalent group of the formula:

where R3=-H, -F or CH3; n is an integer from 0 to 10;

X is a divalent organic group with ether, carbonate or urethane group of the formula: -Y-R4-Y-,

where Y is a bivalent group-O-,-CO-, -COO-, -CONH-R5or R5NHCO-,

R4is a divalent organic group of the formula:

-(CH2)l-where l=2-25, or

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

R5is a divalent organic group of the formula:

-(CH2) n-,

where n=2-8.

Preferred oligomers of structure (I) bifunctional acrylic oligomer represented by the compounds of the formula(1), (2), (3) and (4):

where R1=CH3and R2=N (PFM);

where

Connection 1 (PFM) obtained by direct esterification of α,ω-oligodendrogenesis (meth)acrylic acid (hereinafter, (meth)acrylate means that this refers to both acrylates and methacrylates).

Connection (2)-(4) was synthesized by the reaction macrodiisocyanate based oligomerization-α,ω-diol with a molecular weight of about 1400 with monomethacrylates of ethylene glycol (MEG) - OUMA-1 or monoacrylate (Bisomer™ PPA5S) - OUMA-2, or monomethacrylates of polyoxypropyleneglycol (Bisomer™ PPM5S) - OUMA-3.

Among used bifunctional acrylic oligomers can be noted oligocarbonate ACM-2 patterns:

CH2=C(CH3)COO(CH2)2OCOOCH2CH2OCH2CH2OCOO(CH2)2OOCC(CH3)=CH2,

dimethacrylate butanediol and 1.20-eicosanol (DMB n=4 and EDM n=20 respectively):

CH2=C(CH3)COO(CH2)nOOCC(CH3)=CH2,

and diacrylate glaze the Olathe diphenylolpropane PHA n=5-8 patterns:

Other examples of bifunctional acrylic oligomer, in addition to the above, include polyalkyleneglycol di(meth)arylate, such as polyethylene glycol di(meth)acrylate with an average molecular weight of 300-1500, polypropyleneglycol di(meth)acrylate with an average molecular weight 375-700, polytetramethylene di(meth)acrylate with an average molecular weight of 500-1500, and performancematerial di(meth)acrylate with an average molecular weight of 500 to 600.

For the preparation of compositions can be used and mixtures of these bifunctional acrylic oligomers.

Gold polimerizacionnye acrylic composition according to this invention includes an acrylic monomer. This component is necessary to obtain the solution of salt of gold, regulation of the viscosity of the composition and achieve the necessary physical and mechanical properties of the obtained polymer mesh.

Choice of acrylic monomers is not particularly limited and can be used any known compound having a radically polymerizable group such as (meth)acryloyl or (meth)acryloyloxy.

Used in the claimed compositions monomers include unsaturated carboxylic acids and their derivatives, such as methyl methacrylate, butylmethacrylate, benzyl(meth)acrylate, oxypropylation mo is methacrylat, methylthiourea, menzilcioglu, benzyldimethyl and 2-hydroxyethylmethacrylate (MEG) patterns:

CH2=C(CH3)COOCH2CH2OH.

From the point of view of achieving maximum compatibility between the components of the composition and regulation of cell size mesh polymer are preferably used acrylic oligomers patterns:

where R1=-(CH2)2OOCC(CH3)=CH2and/or-CH(CH3)2.

These compounds were obtained by the method developed for the synthesis OUMA-1, but with replacement of 0.37 or 0.63 mole of telogen (MEG) on equimolecular number depolymerization isopropanol (OUMA-4 and OUMA-5, respectively).

For the preparation of compositions can be used and mixtures of these acrylic monomers.

As indicated gold salts may be any capable of fotovosstanovlenie salt of gold. Sol gold can be selected from the group consisting of disulfonate(I) ammonium (NH4)3[Au(SO3)]2, bis(thiosulfate)-Aurat(I) sodium Na3[Au(S2O3)2]·H2O, chloro(triphenylphosphine)-gold(I) [AuCl(PPh3)], soloconsolidation acid H[AuCl4]·n H2O, tetrachloroaurate(III) and potassium (K) [AuCl4], tetrachloroaurate(III) ammonium NH4[AuCl4], tetrachloroaurate(III) n is sodium Na[AuCl 4]·n H2O, tetrabromoethane(III) sodium Na[AuBr4], dicyanoaurate potassium K[Au(CN)2], tetracyanobenzene(III) and potassium (K[Au(CN)4].

The following illustrative examples preferably used three - and tetrahydrate soloconsolidation acid H[AuCl4]·n H2O (n=3 or 4).

As an initiator of photopolymerization can be used benzoin, methyl benzoin ether, butyl benzoin ether, benzophenone, acetophenone, 4,4'-dichlorobenzophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-he, benzylmercaptan, 1-(4-ISO-propylphenyl)-2-hydroxy-2-methylpropan-1-it, 1-hydroxycyclohexyl, 2-isopropylthioxanthone, the bi oxide(2,6-dimethoxy-benzoyl-2,4,4-trimethylpentyl)phosphine oxide) bi(2,4,6-trimethylbenzoyl)phenylphosphine, oxide, 2,4,6-trimethylbenzenesulfonyl or 2-benzyl-2-dimethyl-amino-1-(4-morpholinomethyl)-butanone-1.

You can use one or a combination of two or more photoinitiators.

The following illustrative examples preferably used a mixture (1:1 by weight) diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and 2-hydroxy-2-methylpropiophenone (hereinafter referred to as PHI).

For UV irradiation can be used any known source of UV light such as a mercury lamp, high pressure mercury vapor lamp superhigh pressure mercury the second lamp low pressure, xenon lamp, carbon arc, bactericidal lamp, metalhalide lamp and electrodeless lamps. The exposure time one of these light sources is determined by lamp type, the absorption wavelength and the sensitivity of the initiator of photopolymerization, and the thickness of the polymerized layer.

In most examples below for photochemical initiation was used mercury lamp high pressure power of 1000 W (CES-1000).

Table 1 presents the structure and properties of the major components of the claimed composition.

It was found that when using as gold salts of crystalline HAuCl4you can get solution of hydroxyl-containing acrylic monomers of very high concentrations. For example, in monomethacrylates of ethylene glycol (MEG) solubility HAuCl4is more than 30% wt. This monomer was selected as the active solvent for salts HAuCl4. From the experimental point of view, the optimum was found to be 12%by weight concentration of salt in the MEG, and this solution was then used as a base to create a specific acrylic compositions.

Table 1
The basic properties of the original (meth)acrylic is s
(Meth)acrylateViscosity, centipoised420, g m-3n20D
MEG4.010711.4520
The OUMA-1TPL 29-34°C10951.5000
The OUMA-3>3000010651.4861
The OUMA-4>3000010861.5012
The OUMA-5>3000010781.4992
OKM-216011961.4660
PHA2000011801.5590
DMB4.710201.4580
EDMTPL 115°C -
PFMTPL 25-28°C9981.4640 at 30°C

Upon irradiation of the liquid composition based on the OUMA-1 + MEG + HAuCl4between the quartz glass of unfiltered light Hg-lamp rapid for 3-4 min spending of HAuCl4i.e. is fotovosstanovlenie Au3+to Au0without forming any products that absorb in the visible and near UV regions of the spectrum (Fig.1,a). Upon further irradiation only after quite a considerable induction period (20-25 min) appears absorption in the visible region near 550 nm (figure 1,b), which can be attributed to the band of the plasma resonance of gold nanoparticles, the intensity of which increases during 60-90 minutes it is Obvious that the transfer of gold from solution in nanoparticles and their agglomeration occur quite slowly. As a result of these processes and by photopolymerization of acrylic groups formed elastic film pink-purple color.

As a result of photopolymerization it is possible to obtain a colorless transparent thick films, in which upon further irradiation or heat generated by the absorption band in the visible region of the spectrum. This fact allows us to consider these films as a new medium for recording and the formation when using an external source of irradiation and/or heating element.

Discovered that the polymerization of acrylates significantly inhibited salt of gold or the products of its transformation. Compared with a control sample not containing HAuCl4the rate of polymerization of the composition on the basis of the OKM-5 is reduced by 2-3 times.

On the other hand, the increase in the concentration of photoinitiator to 3.2 and 5% wt. leads to the overlap of the inhibitory effect of HAuCl4and braking reactions recovery HAuCl4samples remain colorless.

Thus, both photo sessions - polymerization of acrylates and recovery of gold while implementing negatively affect each other. However, in all cases, the formed polymer matrix with good mechanical properties, since the curing of acrylates always proceeds much faster than fotovosstanovlenie gold salts.

Processes photovoltaikanlage HAuCl4and generating a plasma resonance band near 580 nm are strongly dependent on the chemical structure of acrylic components and the mesh density of the resulting matrix (figure 2-4 and table 2). Thus, the greatest rate of spending gold salts and the formation of nanoparticles are observed for "loose" grid-based OUMA, while in the rigid grid of the ACM-2, DMB or trimethylolpropane these processes are much less effective. Similarly, in the absorption spectrum is autosoterism "loose" meshes of the OUMA-2-OUMA-4 in the visible region is shown very intense narrow peak of the resonance, but in the spectrum of the polymers of the compositions on the basis of the ACM-2 and DMB completely no absorption in the visible region, i.e. the grid cells of these polymers by size are not large enough to include gold nanoparticles.

Table 2
Gold acrylic composition and some properties of the films - products of photochemical reactions (compositions in wt.% wherever not specified: acrylate - 74, a solution of HAuCl4in MAG - 25, photoinitiator - 1)
Oligomerk 102with-1λ, nmExample
The OUMA-12.53580/64013
After 14 days--25
+ 5% GDMA-62526
The OUMA-32.51580/62015
The OUMA-4- 57016
The OUMA-5-56017
OKM-21.6656018
After 7 days--27
5% HAuCl4--28
PHA0.37-19
DMB-580/62020
EDM-21
PFM-60022
Notes: k is the rate constant of fotorazlozheniya HAuCl4;
λ is the position of the band maximum plasma resonance

The presence utverzhdenii acrylic matrix particles of gold Nanomet the new range shown by electron microscopy (figure 5). The number of nanoparticles is increased after heat treatment of the sample, while heated above the glass transition temperature of the matrix leads to the secondary formation of fine particles of gold.

The proposed spatial gold-mesh polymer material was obtained as follows.

First prepare a solution of gold salts, preferably HAuCl4in the acrylic monomer, preferably hydroxyl-containing, in a concentration of 5-30% wt.

To bifunctional acrylic oligomer (or a mixture of several oligomers) or, in some cases, its a mixture of acrylic monomer is added the calculated (on the total weight of the acrylates) number of photoinitiator.

Mix both solution and placed in a mold made of glass (silica or silicate), is irradiated with light UV lamp for conducting three-dimensional free-radical polymerization of acrylates and restore gold salts and receive a colorless and transparent glass-like material.

The claimed method of the received spatial-mesh polymer material containing gold in the zero valence and characterized by the ability to generate in the range of 500-650 nm band plasma resonance of gold nanoparticles during thermal or fotomodelli. This property of this material allows you to record and store information local effects such as laser beam, or use a pattern mask on the surface and the volume of the material.

Figure 6 shows a photograph of the surface of the specified material with the image obtained by irradiation of a UV lamp high pressure 1000 watts through an opaque mask of a given shape, and figure 6,b shows the raster obtained with the heated pattern.

The following examples more specifically describe the subject matter of this invention but not to limit possible implementations of the invention.

Synthetic example A. Synthesis of algorithmically the OUMA-1

500 g (0.5 mole) oligomerisation-α.ω-diol diisocyanate (Mn≈1000), 140.8 g (1.1 mol) of monomethacrylate of ethylene glycol (MEG) and 9.0 g of AllowOverride stirred at room temperature for 12 hours until complete consumption of the isocyanate groups in the IR spectra. Yield ~100%. Mn≈1400; Mw≈1600; Mw/Mn≈1.2; functionality ~2, d420=1086 kg·m-3n20D=1.5027.

Synthetic examples B and C. the Synthesis oligourethane(meth)acrylate, the OUMA-2 and OUMA-3

Algorithmically the OUMA-2 and OUMA-3 is obtained from 500 g (0.5 mole) oligomerisation-α.ω-diol, diisocyanate according to the method of Synthetic example And using instead of MEG 1.1 mole of telogen - "Bisomer™" PPA5S (423.6 g) or Bisomer" PPM5S™ (398.2 g), respectively.

Synthetic examples of Mr. E. Synthesis oligourethane is Krylatov ON-4 and OUMA-5

The oligomers obtained from 500 g (0.5 mole) oligomerisation-α.ω-diol, diisocyanate according to the method of Synthetic example And using a mixture Tulegenov MEG and isopropanol:

The OUMA-4: 0.63 and 0.37 mol MEG and isopropanol, respectively;

The OUMA-5: 0.37 and 0.63 mole MEG and isopropanol, respectively.

Preparatory example 1. Preparation of the solution tetrahydrate soloconsolidation acid in MEG

In a bottle of dark glass dissolving 0.03 g HAuCl4*4H2O (0,073 mmole) of 0.22 g MEG (or 0.38 mmole) and get a solution with a salt concentration of 12 wt.%. in terms of HAuCl4. The solution was stored in the dark at a temperature of 8-10°C and then used for obtaining acrylic compositions.

Preparatory example 2. Preparation of the solution of three-hydrate soloconsolidation acid in MEG

In a bottle of dark glass dissolve 0,029 g HAuCl4*3H2On (0,073 mmole) of 0.22 g MEG (or 0.38 mmole) and get a solution with a salt concentration of 12 wt.%. in terms of HAuCl4. The solution was stored in the dark at a temperature of 8-10°C and then used for obtaining acrylic compositions.

Preparation of gold-containing oligomeric compositions

Example 1

In a bottle of dark glass to a mixture of 0.74 g of diacrylate the OUMA-1 and 0.01 g of photoinitiator Dracur 4265 (a mixture of 1:1 diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and 2-hydroxy-2-methylpropiophenone is on) in an amount of 1 wt.%. to the total weight of acrylates with vigorous stirring, 0.25 g of a solution of HAuCl4in MEG in preparatory example 1, i.e. compositions contain 3,0% HAuCl4.

Examples 2-10

According to the method of example 1 obtained gold oligomeric compositions on the basis of the following acrylates: OUMA-2, OUMA-3, OUMA-4, OUMA 5 OKM-2, PHA, DM, EDM and PFM (table 1), respectively.

Examples 11, 12

According to the method of example 1 prepared 2 control sample analogues of the compositions of examples 1 and 8, but not containing HAuCl4.

The spatial-mesh polymer material containing gold in the zero valence

Example 13

1.0 g of the composition of example 1 is applied to the plate of quartz or silicate glass size 75×35 mm with sealing gasket thickness of 0.09 mm Form serves a second glass plate, and the Assembly is irradiated with a mercury lamp Jack Russell 1000 for 2 min on each side of the sample.

Examples 14-24

According to the method of example 13 is obtained gold-bearing polymeric material of the compositions in examples 2-12, respectively.

Example 25

According to the method of example 13 is obtained gold-bearing polymeric material of composition 1 after aging for 14 days at 5-7°C.

Example 26

According to the method of example 13 is obtained gold-bearing polymeric material of composition 1, in which additional is but put 5% wt. reductant - glycidylmethacrylate.

Example 27

According to the method of example 13 is obtained gold-bearing polymeric material of composition 6 after aging for 7 days at 5-7°C.

Example 28

According to the method of example 13 is obtained gold-bearing polymeric material of composition 8 with the difference that the content of HAuCl4increased to 5% wt.

Illustrative examples of recording information using the proposed spatial-mesh polymer material containing gold in the zero valence

Illustrative example 1

The film of polymer material obtained in example 13, size 40×15×0.5 mm was put a metal grate with a hole diameter of 200 microns and the Assembly was irradiated through the grille Hg-lamp Jack Russell 1000 within 2 minutes On the film surface appeared the image of the lattice in the form of red-purple discs (6,a).

Illustrative example 2

According to the method of example 13 is obtained a clear, colorless film of polymeric material, at which point the heating element with a temperature of 100-130°C caused an arbitrary image (Fig.6,b).

1. Gold polimerizacionnye acrylic composition for the manufacture of polymeric recording medium for optical recording of information, consisting of:
(1) 20-80 parts by weight of a bifunctional acrylic oligomer, (methacrylic groups which are linked divalent organic group with an ether, carbonate or urethane group,
(2) 20-80 parts by weight of acrylic monomer selected from the group of alkyl(meth)acrylates or oxyalkyl(meth)acrylates, where the alkyl is lower alkyl,
(3) 5-25 parts by weight of gold salts selected from the group of inorganic salts of gold, soluble in the specified acrylic monomer,
(4) 0.1 to 3 parts by weight of photoinitiator.

2. Gold polimerizacionnye composition according to claim 1, characterized in that the bifunctional acrylic oligomer has the following structure:

where R1=-H, -F or CH3; R2is a divalent group of the formula:

where R3=-N or CH3; n is an integer from 0 to 10; X is a divalent organic group with ether, carbonate or urethane group of the formula: -Y-R4-Y-, where Y is a bivalent group-O-, -CO-, -COO-, -CONH-R5or R5NHCO-,
R4is a divalent organic group of the formula:
-(CH2)l-where l=2-25,

where n is an integer from 1 to 3, m is an integer from 1 to 250;
R5is a divalent organic group of the formula: -(CH2)n-,
,,
where n=2-8.

3. Gold polimerizacionnye composition according to claim 1, characterized in that the AK is silt monomer has the following structure:

,
where R1=-H, -F or CH3; R3=-H or-CH3; n is an integer from 0 to 10, or
,
where R1=-H, -F or CH3; R7= alkyl2-C20or -(CH2)nIs HE, where n=2-8.

4. Spatial-mesh polymer material containing dissolved gold in the zero valence, which is a product of the irradiation of gold polimerizacionnye acrylic composition according to any one of claims 1 to 3, are capable of when external heat and/or fotomodelli to the generation of the plasma resonance band in the visible region of the spectrum formed gold nanoparticles.

5. Spatial-mesh polymer material according to claim 4, characterized in that it is a colorless and transparent glass-like material with an optical transmittance in the visible spectral range not lower than 90%.

6. Spatial-mesh polymer material according to claim 4 or 5, characterized in that it is a recording medium for optical information recording and gives a point-response in the field 500-640 nm at local thermal and/or fotomodelli.

7. A method of obtaining a spatial-mesh polymer material containing dissolved gold in the zero valence, according to any one of claims 4 to 6, comprising the following stages:
(1) PR is the expansion of the solution of salt of gold acrylic monomer;
(2) preparation of gold polimerizacionnye acrylic composition according to claim 1 by mixing the salt solution gold acrylic monomer with a bifunctional acrylic oligomer and photoinitiator;
(3) pathobiochemie composition in the form of quartz or silicate glass.



 

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FIELD: chemistry.

SUBSTANCE: invention relates to photorefractive material and may be used in optoelectronic devices, dynamical hologram recording and other photonic technologies. Mixed oxide of La1-xSrxYO3-δ formula, where 0.1 ≤ x ≤ 0.27, is described as photorefractive material. Also, bath for production thereof is described. It contains yttrium oxide, strontium carbonate and lanthanium yttriate, ratio of components being as follows (wt %): LaYO3 - 64.32-85.71; Y2O3 - 4.76-23.79; SrCO3 - remainder to 100.

EFFECT: higher photorefractive effect of material.

2 cl, 3 ex

The invention relates to methods of producing a photosensitive layer of lead sulfide, which is used in the manufacture of semiconductor devices sensitive to infra-red radiation
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FIELD: chemistry.

SUBSTANCE: invention relates to an acrylic composition for plugging threaded joints, particularly for fixing high frequency connectors of inter-block cables. The acrylic composition consists of an acrylic amide-containing resin, an organic colour pigment and a solvent. The acrylic amide-containing resin is a copolymer of butylmethacrylate and acrylamide. The solvent used is a mixture of acetone, xylene and butylacetate. The acrylic composition has high adhesion to different metals, long working life and a wide range of working temperature from minus 40 to plus 50°C. The composition can be used on vertical surfaces.

EFFECT: use of the composition prevents self-unfastening of low-loaded threaded joints subjected to vibration loads and, if needed, enables dismantling of assembled elements.

1 ex

FIELD: chemistry.

SUBSTANCE: disclosed aqueous dispersion of copolymerisation products containing A) one or more hydroxy-functional copolymerisation products, obtained from the following (wt %): non-hydroxyl containing ester of (meth)acrylic acid and/or vinylaromatic compounds (53.5-87), hydroxy-functional ester of (meth)acrylic acid (2.5-45.9), ionic and/or potentially ionic monomers (0.6-19) capable of radical copolymerisation, as well as, if necessary, other monomers capable of radical copolymerisation which are different from compounds of components a)-c) (0-43.4) and B) at least one hydroxy-functional polycarbonate-polyol as a reactive diluent. Disclosed also is an aqueous coating agent which contains one or more of the disclosed aqueous dispersions of copolymerisation products and at least one cross-linking agent which interacts with hydroxyl groups.

EFFECT: disclosed aqueous dispersions have low solvent content and enable to obtain coatings with high level of resistance of lacquer films, with high scratch resistance and acid resistance.

5 cl, 1 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: polymer material contains acrylic polymer, chlorine-containing polymer and inorganic hydroxide. The acrylic polymer is selected from a homopolymer of alkyl(alc)acrylate or copolymer of alkylmethacrylate and alkylacrylate. The chlorine-containing polymer contains 5-70 wt % halogen. The inorganic hydroxide is selected from magnesium hydroxide, zinc hydroxide or mixtures thereof, except a mixture of magnesium hydroxide and zinc oxide or magnesium hydroxide and zinc stannate. Weight ratio between the chlorine-containing polymer and the acrylic polymer is at least 0.3. Polymer material is obtained by mixing the chlorine-containing polymer and inorganic hydroxide in molten acrylic polymer. The polymer material is used to make articles and structural elements in construction.

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45 cl, 3 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to use of granular polyalkyl(meth)acrylate polymers with average particle size V50 from 30 to 70 mcm for increasing fatigue cracking resistance, which contain polyalkyl(meth)acrylate of moulding compounds. The invention proposes use of granular polyalkyl(meth)acrylate polymers with average particle size V50 from 30 to 70 mcm in a moulding compound, containing at least 65 wt % of an impact viscosity modifier obtained beforehand which contains at least one polyalkyl(meth)acrylate phase, at least 8 wt % of the said granular polyalkyl(meth)acrylates and from 0 to 20 wt % polyalkyl(meth)acrylates with molecular weight between 20000 and 350000 g/mol, whereby the sum of wt % of the components a) - c) is equal to 100 wt % to increase fatigue cracking resistance of said moulding compounds. Disclosed also are moulding compounds described above and corresponding moulded articles.

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23 cl, 1 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polymer mixtures for making shock resistant moulded articles. The disclosed polymer mixture for making moulded articles which contains (meth)acrylate (co)polymer components with different molecular weight and viscosity of solution in chloroform, and an impact viscosity modifier based on cross-linked poly(meth)acrylates, having a nucleus/shell/shell structure, whereby the test sample made from the polymer mixture simultaneously possess the following characteristics: Young's modulus of elasticity (ISO 527) of at least 2500 MPa, Vicat softening point VET (ISO 306-B50) of at least 110°C, impact viscosity (ISO 179-2D, perpendicular the layers) of at least 30 kJ/m2, flow melt index MVR (ISO 1133, 230°C/3.8 kg) of at least 1.0 cm3/10 min. The invention also discloses articles injection moulded from the said polymer mixture, use of the polymer mixture to obtain moulded articles and versions of using the obtained moulded articles.

EFFECT: design of thermoplastic material with a balanced profile of characteristics.

14 cl, 1 tbl, 5 ex

FIELD: chemistry.

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EFFECT: material enables to make articles with better mouldability, impact viscosity of the material increases 2-3 times compared to existing materials.

4 cl, 1 tbl, 21 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: declared invention concerns hydrogel compositions useful as a dressing material or protective agent, and for application of a wide range of active substances in relation to the skin and tissues of mucosas, such as mouth, including tooth bleaches. The faza-parted, film-forming composition containing an admixture is offered: (a) the first polymer bulking up in water, and the specified polymer is not dissolved in water at pH less than approximately 5.5, or water-soluble polymer; (b) an admixture of hydrophylic polymer and additional low-molecular polymer, capable to formation of hydrogen communications with hydrophylic polymer; (c) the second polymer bulking up in water, and the specified polymer we will not dissolve in water at all value pH; and (d) unessential active substance, in a dissolvent or in an admixture of dissolvents where the composition is exposed to separation of phases at hydration.

EFFECT: treatment of a disease state of various surfaces of a body (teeth, fingernails, skin, mucosas etc).

44 cl, 7 ex

FIELD: medicine.

SUBSTANCE: composition contains water-swelling, water-insoluble polymer, mixed hydrophilic polymer and complementary oligomer able to form hydrogen bond with hydrophilic polymer, and a bleaching agent, preferentially peroxide. The composition is applied a dental bleaching composition and applied on teeth to be bleached, and then removed as the required bleaching is reached. In best versions the composition is unstable and translucent. There are also methods of preparation and application of the compositions.

EFFECT: reduced dental sensitivity and damage or irritation of gums and oral mucous membranes, improved clinical effectiveness.

54 cl, 10 ex

FIELD: chemistry.

SUBSTANCE: proposed method of producing a water and oil repellent agent involves emulsification of (a) 15-85 wt % perfluoroalkylethylacrylate, (b1) 5-65 wt % 2-ethylhexylmethacrylate and (b2) 1-40 wt % benzyl methacrylate in the presence of (c) a cation surface active substance of the polyethylene oxide adduct type, or neutralised organic acid compound of an amine, with polyethylene oxide chains, and (d) compounds based on polypropylene glycol, with molecular weight 300-3000, or hexylene glycol, with subsequent copolymerisation reaction in the presence of a polymerisation initiator, and mixing the obtained aqueous dispersion with (e) blocked isocyanate.

EFFECT: satisfactory water and oil repellent for synthetic and natural fibre.

5 cl, 22 ex, 5 tbl

FIELD: chemistry.

SUBSTANCE: invention refers to technology of hull-kernel particles which can be used to modify impact strength of poly(met)akrylate moulding compositions. According to method a) water and emulsifier b) are added with 25.0 to 45.0 mass fractions of the first composition containing A) alkylmetacrylate 50.0 to 99.9 mass fractions, B) alkylakrylate 0.0 to 40 mass fractions, C) cohesive monomers 0.1 to 10.0 mass fractions, and D) styrene monomers 0.0 to 8.0 mass fractions, and polymerised, c) added 35.0 to 55.0 mass fractions of the second composition containing E) (met)akrylates 80.0 to 100.0 mass fractions, F) cohesive monomers 0.05 to 10.0 mass fractions, and G) styrene monomers 0.0 to 20.0 mass fractions, and polymerised, d) added 10.0 to 30.0 mass fractions of the third composition containing H) alkylmetakrylates 50.0 to 100.0 mass fractions I) alkylakrylates 0.0 to 40.0 mass fractions and J) styrene monomers 0.0 to 10.0 mass fractions, and polymerised. Method is distinctive in that e) each polymerisation cycle is performed at temperature within 60 to 90°C and f) fractional content of all substances is selected so that total weight A) to J) per total weight of aqueous dispersion exceeds 50.0 mass %. Presented method is used to produce impact strength modifiers minimum content of which provides sufficient improvement of impact strength when tested on cut moulding composition samples, not degrading at the same time other important properties of moulding composition.

EFFECT: production of impact strength modifiers minimum content of which provides sufficient improvement of impact strength when tested on cut moulding composition samples, not degrading at the same time other important properties of moulding composition.

17 cl, 8 tbl

FIELD: chemistry.

SUBSTANCE: disclosed aqueous dispersion of copolymerisation products containing A) one or more hydroxy-functional copolymerisation products, obtained from the following (wt %): non-hydroxyl containing ester of (meth)acrylic acid and/or vinylaromatic compounds (53.5-87), hydroxy-functional ester of (meth)acrylic acid (2.5-45.9), ionic and/or potentially ionic monomers (0.6-19) capable of radical copolymerisation, as well as, if necessary, other monomers capable of radical copolymerisation which are different from compounds of components a)-c) (0-43.4) and B) at least one hydroxy-functional polycarbonate-polyol as a reactive diluent. Disclosed also is an aqueous coating agent which contains one or more of the disclosed aqueous dispersions of copolymerisation products and at least one cross-linking agent which interacts with hydroxyl groups.

EFFECT: disclosed aqueous dispersions have low solvent content and enable to obtain coatings with high level of resistance of lacquer films, with high scratch resistance and acid resistance.

5 cl, 1 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polymer composite materials, particularly a method of producing a nanocomposite based on a liquid crystal polymer and an inorganic semiconductor which can be widely used in laboratory experiments and in industry. The invention discloses a method of producing a nanocomposite which involves mechanical treatment of a solution of a liquid crystal polymer of the type poly-4-(n-acryloyloxyalkoxy)benzoic acid of formula: , where n=3-12, until interchain bonds of the polymer break.The solution is mixed with nanoparticles of the inorganic semiconductor coated with a low-molecular weight organic ligand which contains the same functional group as the polymer and is selected from a group of fatty acids. The obtained mixture is held, chemically bonded nanoparticles are formed and separated and the solvent is distilled off. The inorganic semiconductor used is cadmium selenide, cadmium sulphide or lead sulphide. The fatty acid used is oleic or palmic or linoleic acid.

EFFECT: disclosed method enables to obtain nanocomposites based on liquid crystal polymers which contain nanoparticles of inorganic semiconductors which are included in the volume of the composite in an ordered manner.

2 cl, 4 dwg, 3 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: declared invention concerns hydrogel compositions useful as a dressing material or protective agent, and for application of a wide range of active substances in relation to the skin and tissues of mucosas, such as mouth, including tooth bleaches. The faza-parted, film-forming composition containing an admixture is offered: (a) the first polymer bulking up in water, and the specified polymer is not dissolved in water at pH less than approximately 5.5, or water-soluble polymer; (b) an admixture of hydrophylic polymer and additional low-molecular polymer, capable to formation of hydrogen communications with hydrophylic polymer; (c) the second polymer bulking up in water, and the specified polymer we will not dissolve in water at all value pH; and (d) unessential active substance, in a dissolvent or in an admixture of dissolvents where the composition is exposed to separation of phases at hydration.

EFFECT: treatment of a disease state of various surfaces of a body (teeth, fingernails, skin, mucosas etc).

44 cl, 7 ex

FIELD: medicine.

SUBSTANCE: composition contains water-swelling, water-insoluble polymer, mixed hydrophilic polymer and complementary oligomer able to form hydrogen bond with hydrophilic polymer, and a bleaching agent, preferentially peroxide. The composition is applied a dental bleaching composition and applied on teeth to be bleached, and then removed as the required bleaching is reached. In best versions the composition is unstable and translucent. There are also methods of preparation and application of the compositions.

EFFECT: reduced dental sensitivity and damage or irritation of gums and oral mucous membranes, improved clinical effectiveness.

54 cl, 10 ex

FIELD: chemistry.

SUBSTANCE: proposed method of producing a water and oil repellent agent involves emulsification of (a) 15-85 wt % perfluoroalkylethylacrylate, (b1) 5-65 wt % 2-ethylhexylmethacrylate and (b2) 1-40 wt % benzyl methacrylate in the presence of (c) a cation surface active substance of the polyethylene oxide adduct type, or neutralised organic acid compound of an amine, with polyethylene oxide chains, and (d) compounds based on polypropylene glycol, with molecular weight 300-3000, or hexylene glycol, with subsequent copolymerisation reaction in the presence of a polymerisation initiator, and mixing the obtained aqueous dispersion with (e) blocked isocyanate.

EFFECT: satisfactory water and oil repellent for synthetic and natural fibre.

5 cl, 22 ex, 5 tbl

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