The water dispersion of silicone elastomer with variable transmission and method of reception

 

(57) Abstract:

Describes the water dispersion of silicone elastomer with variable transmission and method of reception. Aqueous dispersion based on silicon compounds and organic(fir) (co)polymers having crosslinking ability by removing water by drying in ambient conditions with obtaining elastomer, having adjustable light transmission and superior mechanical characteristics, differs in that it does not contain any reinforcing mineral fillers and contains the following components: (A) an emulsion of the type oil-in-water, consisting of 100 weight.h. oil or ,-(dihydroxy)polydiorganosiloxane polymer (A1) and 1-100 weight.h. organosilicon crosslinking agent (A2), stabilized by at least one surface-active agent (A3) selected from anionic and nonionic surfactants and mixtures thereof; and this emulsion consists of particles with a size of 0.1 (100 nm - 100 μm (100 000 nm) with a dry matter content of at least 60 wt.% (C) per 100 weight.h. oil or polymer (A1) from 1 to 100 weight.h. aqueous dispersions of at least one organic (co)polymer having a particle size of 0.01 (10 nm) - 10 masatora curing at 100 weight.h. oil or polymer (A1). Get the water dispersion is added to the emulsion (a) dispersion (B), then the curing catalyst (C) when the ambient temperature. The technical result is the possibility of obtaining elastomer with controlled light transmission and improved mechanical characteristics. 2 C. and 16 h.p. f-crystals, 2 tab.

The invention relates to aqueous dispersions based on silicones and organic latex(fir) (co)polymer(ROS), and specified aqueous dispersion capable of forming cross-linked structure in the elastomer, with adjustable light transmission through the removal of water by drying in ambient conditions. The invention relates also to method of obtaining and applying the specified dispersion in the construction industry for the production of silicone elastomer products with variable transmission, in particular for the production of sealing mastic (llers), putties, protective coatings, coating materials to be applied on the facades of buildings.

The prior art and described aqueous dispersions based on silicones, are able to create a cross-linked structure in the elastomers with sweeeeeet basic aqueous dispersion, which is a mixture of the following components: (i) silicone microemulsion with a particle size of less than 0.15 μm (150 nm) obtained by polymerization in emulsion of cyclopolymerization with (2i) 5-30 weight. parts (per 100 parts of the silicone polymer) colloidal silica and (3i) with 1-5 weight parts (per 100 parts of the silicone polymer) catalyst type in primary forms dialkylamino. Another patent EP-A-0542498 describes the basic aqueous dispersion, which is a mixture of: (i) water emulsion of cross-linked silicone polymer which is the product of cross-linkage silicone oil having silanol end groups, using alkoxysilane in the presence of a catalyst based on tin, in which less than 10% of the particles have a size greater than 1 μm (1000 nm), C (2i) 0.7 to 2 parts by weight (per 100 parts by weight of cross-linked silicone polymer) special surface-active agent, consisting of alkylsulfate alkali metal or ammonium, with the component (3i), applied with the aim of obtaining an elastomeric product having such mechanical properties that allow it to be used in building materials industry, namely: 2.5 to 45 weight parts per 100 weight of the rum particles less than 0.06 μm (60 nm).

These aqueous dispersions, are able to structure in cross-linked structure translucent elastomers have, unfortunately, a number of disadvantages, among which we should mention the following:

their storage stability is low, because these dispersions show a tendency to the formation of gel in the premature development of condensation reactions. These reactions can occur between the silicone polymer and colloidal silicon dioxide, which is active due to the presence of surface hydroxyl groups,

- the achieved level of light transmission is controlled mainly only by regulating the percentage of the loaded silicon-containing component, although it is well known that any fluctuations in the percentage of silicon dioxide can significantly modify some basic properties of the elastomer, in particular its mechanical tensile strength, elasticity and ability to adhesion. Therefore, dispersion in the above patents do not allow you to adjust the transparency of the elastomer without changing at the same time some of its main properties.

According to the present invention has established that ASIC chemically active ingredients, such as colloidal silicon dioxide, and

- the ability to cause cross-linked structuring elastomer by removal of water. This last fact has a double advantage: on the one hand, it is possible to achieve a controlled light transmission regardless of other qualities of the elastomer, in particular its mechanical properties, and, on the other hand, despite the absence of a reinforcing mineral fillers, it is possible to achieve improved mechanical properties, and this fact is especially valuable for further use of elastomers in the manufacture of building materials.

Both of these above-mentioned advantages can be achieved by replacing the mineral fillers that are commonly used in conventional aqueous dispersions intended for structuring silicone elastomers by removing water, a polymeric filler in the form of a water dispersion of organic(fir) (co)polymer(ROS).

In the context of the present invention, the expression "adjustable light transmission" means that the level achievable light transmission easy regulation in the whole range of values for this parameter are: from full the properties, referred to in the present description, are those properties that are necessary to ensure that the product elastomer can perform its function of sealing gaskets for joints, regardless of the climatic conditions of its operation. More specifically, we are talking about the following properties: scensny modulus at 100% elongation, elongation at break, tear resistance and elasticity and ability to adhesion.

The fact of the use of a combination of silicone (silicone) and organic latex already described in the patent EP-A-0410899. This technique allows to increase the content of dry extract, while maintaining sufficient viscosity in aqueous silicone dispersions of the type dispersions which contain reinforcing mineral Supplement. In the result by removing water get elastomeric products, which are completely opaque (non-transparent), but have improved mechanical properties.

None of the publications known from the prior art, does not speak about the possibility of the application of which is the aim of the present invention, namely the use of the additive polymer filler to obtain elastomeric products with adjustable transparency for construction purposes, being the of fillers.

More specifically, the present invention relates to a water dispersion based on silicones and organic(fir) (co)polymer(ROS) with the potential to cause cross stitched structuring by removing water by drying in ambient conditions, to obtain elastomer with variable transmission and having improved mechanical properties. Specified aqueous dispersion according to the invention differs in that it is devoid of any reinforcing mineral fillers fact that it contains the following components:

(A): the emulsion of the type oil-in-water, consisting of 100 weight parts of the oil or ,- (dihydroxy)polydiorganosiloxane polymer (A1) and from 1-100 weight. parts of silicon structuring agent (A2), and this emulsion:

- stabilized with at least one surfactant (A3) selected from among anionic agents, nonionic agents, and mixtures thereof,

- consists of particles with a size of 0.1 μm (100 nm) to 100 micrometers (100000 nm),

- has a dry matter content of at least 60 wt.%,

(B): 100 weight. parts of oil or polymer (A1) from 1 to 100 weight. parts of the water dispersion of at least one organic (co)poligo substances from 10 to 70 wt.%,

(C): if necessary, per 100 weight. parts of oil or polymer (A1) is from 0.01 to 5 weight. parts of the connection metal acting as a catalyst,

moreover, the mentioned aqueous dispersion has a dry matter content of at least 60 wt.%; regulation of light transmission elastomeric product in the process of getting it is at the stage of obtaining a water dispersion through regulation required(IIR) values (magnitudes) of the following parameters: either by adjusting the particle size of the polymer latex (B), or adjusting the refractive index of the polymer, which is part of the latex (B), by varying the chemical composition of organic (co)polymer, or by adjusting both of these parameters: the particle size and refractive index.

The final aqueous dispersion receive simple homogeneous mixing of all components to obtain a homogeneous dispersion, which is stable during storage, if it is protected from access of air.

Any expert in the art knows that the diffusing capacity of the particles (in our case, the particles of polymer latex (B)) in the dispersion medium (in our case silicone matrix, policier, i.e., the controlling parameter is inversely proportional to the light transmission elastomer), decreases as:

- increase the size of the particles,

- differences of the refractive indices of the particles and the dispersion medium.

All of the above is confirmed by the law of diffusion of RELIGA (RAYLEIGH), according to which the diffusing ability of the Pd particles is expressed by the equation:

< / BR>
where x = 2r, where r = average radius of the particle, = wavelength of light, m = n1/n2, n1 = the refractive index of the particles, and n2 = the refractive index of the dispersion medium.

EMULSION (A):

Oil or polymer (A1):

Source-(dihydroxy)polydiorganosiloxane should have a viscosity of at least 100 mPas at 25oC, preferably at least 50000 mPas.

In fact, when the values of viscosity in excess of 50000 mPas, get elastomer that combines the whole complex of the desired mechanical properties, particularly elongation and tensile strength. In addition, there is another consideration: the higher the viscosity, the more stored mechanical properties during aging of the elastomer.

For the purposes of the present invention, the preferred value of viscosity of 50,000 - 1,500,000 mPas at 25oC.

Organic radicals -- (dihydroxy)polydiorganosiloxane are monovalent hydrocarbon radicals containing up to 6 carbon atoms, possibly substituted cyanide or fluoride groups. The substituents are typically selected for their availability and that of industrial products containing methyl-, ethyl-, propyl-, phenyl-, vinyl and 3,3,3-triptoreline radicals. In General, at least 80% of these radicals represented by methyl radicals.

A crosslinking agent (A2):

As mentioned above, in the present invention involved organosilicon crosslinking agent. Below is a list of recommended cross-linking agents, and each of these agents) exact recommended amount of them in the emulsion (A) considering the nature of each specific recommended cross-linking agent. These recommended quantities are expressed in parts by weight per 100 parts of oil or polymer (A1):

- 1-15 weight. parts of organosilicon compounds

- 1-100 weight. parts of microemulsion casinocasinooy resin according to the patent US-A-3355406 and 3433780,

- 5-100 weight. parts of the reactive silicone resin having a low molecular ve the molecular weight and insoluble in toluene,

- 5-100 weight. parts gidroksilirovanii silicone resin, each molecule of which contains at least two different element selected from among units of the formula: R3Si0,5(M), R2SiO(D), RSiO1,5(T) and SiO2(Q), R is generally an alkyl radical containing 1-6 carbon atoms, vinyl and 3,3,3-cryptocaryon and having a weight content of hydroxyl groups of from 0.1 to 10%. Among these resins, are introduced into the process in their original form or in the form of aqueous emulsions, can be called tar brands MQ, MDQ, TD and MTD,

- 1-20 weight. parts of a silane having the formula: RaSiX4-ain which R is a monovalent organic radical, in particular the stands or vinyl, a = 1 or 0, and X is condensed and/or hydrolyzable group, preferably selected from among alkoxy groups, acyloxy, climinax, alkylamino, amido, alkenylacyl and their various possible mixtures. In the case when X is alkoxy, it is desirable to add as a stabilizer 2-amine-2-methylpropanol, as it recommends the patent EP-A-0259734.

A crosslinking agent (A2), preferably used in the present invention, is the addition of 5-100 parts gidroksilirovanii silicone resin mentioned above.

Involved in this invention, the surfactant can be nonionic. As examples of fatty alkoxysilane acid, polyalkoxysiloxanes ALKYLPHENOLS, polyalkoxysiloxanes fatty alcohols, polyalkoxysiloxanes or polyglycerol fatty amides, polyglycerols alcohols and diols, block polymers of ethylene oxide/propylene oxide, polydiorganosiloxane containing siloxane units as carriers of sequences of ethylene oxide or propylene oxide, and Alkylglucoside, alkylpolyglucoside, ethers, sugars, sugar esters, sharolaid, esters sorbitan, ethoxylated compounds of these derivatives of sugars and their mixtures. Preferred nonionic surfactants are polyalkoxysiloxanes ALKYLPHENOLS and polyalkoxysiloxanes fatty alcohols.

As the on-active(ing) agent(agent) to one (or more) is preferred(reference) anionic(tion) surfactant(tion) agent(agent).

Surface-active agents, taken singly or in mixture, are chosen depending on the nature of oil or silicone polymer (A1), which will emulsify. In this case, the hydrophilic-lipophilic balance HLB choose from 11 to 15 in order to emulsify the oil or polymer (A1), consisting of one- (dihydroxy)polydiorganosiloxane.

OBTAINING EMULSION (A):

To obtain emulsion (A) you can use the method of emulsion polymerization, because in this way it is possible directly to obtain the emulsion. In addition, this method allows the flexibility to obtain emulsion (A) containing a high-viscosity ,- (dihydroxy)polydiorganosiloxane.

According to this method, the emulsion of the type oil-in-water silicone phase is obtained by anionic polymerization of the oil (A1) having a small viscosity of 100 mPas to 1000 mPas. Optionally, the polymerization can be carried out in the presence of a crosslinking agent (A2), which - according to another variant of the method - you can add and later, upon completion of the polymerization. This method of anionic polymerization is described in U.S. patent US-A-2891920 detail and especially US-A-3294725 (shown here as a reference). Proceedural is (as it recommends the patent US-A-3294725) salt of an alkali metal and an aromatic sulfonic acid, and the free acid thus acts also as a catalyst for polymerization. The catalyst and surface active agent are preferably dodecylbenzenesulfonic acid and its salts with alkali metals, in particular its sodium salt. If necessary, you can also add other surface-active agents of the anionic or nonionic type. However, this additive is not necessary, as in the patent US-A-3294725 noted that the number of anionic surface-active agent resulting from the neutralization of sulfonic acid, sufficient to stabilize the emulsion polymer. Usually this number is less than 3%, preferably 1.5% by weight, of the weight of the emulsion (A).

According to the present invention it is preferable, however, to use as starting compounds are polymerized ,- (dihydroxy)polydiorganosiloxane, and then translate it in water emulsion in the presence of a crosslinking agent (A2), then the resulting emulsion stabilizing anionic and/or nonionic surface-active agent in the manner well known to any person skilled in the art and are described in detail in the literature (see, for example, patent FR-A-2064563, FR-A-2094322, F is reorganisation (A1) with a crosslinking agent (A2) and with anionic and/or nonionic surface-active agent (A3), the latter can be used in aqueous solution, and then, if necessary, add water and transfer all the mixture in a fine and homogeneous emulsion by passing it through a classical colloid mill. If necessary, the resulting milled mass can be diluted with additional water. The result is an emulsion (A), stable anionic and/or nonionic surface-active agent and persistent storage.

Emulsion (A) obtained by the emulsion polymerization or by transferring the emulsion of the silicone polymer (A2) is an emulsion of the type oil-in-water having a dry matter content equal to or greater than 60 wt.% and preferably equal to from 80 to 98 wt.%.

In this regard, it should be noted that the transfer operation in the state of emulsions of very viscous silicone polymer (A1), whose viscosity exceeds 30000 mPas, can be successfully done by using the method described in the publication WO-A-94/09058 (shown here as a reference). The advantage of this method is that it allows very accurately maintain the desired ratio of the viscosities of the aqueous phase, on the one hand, and the silicone phase with the other. Neobhodimosti method of emulsion polymerization or the preferred method of transfer in emulsion, carrying out this polymerization or transfer in emulsion directly in the presence of the rubber latex (B) and on the basis, in whole or in part, of the components (A1) and (A2).

THE DISPERSION OF THE LATEX (B):

Latex (B):

Latex (B) receive from the aqueous suspension of polymer particles, and found the suspension to be obtained by way of emulsion (co)polymerization polymerizing(IIR) organic(fir) monomer(ROS).

The principal polymerizing monomers suitable for implementing the present invention includes at least one basic monomer selected from: styrene (a), butadiene (b), complex acrylic esters (c) vinyl NITRILES (d). The term "complex acrylic esters" in this case denotes esters of acrylic acid and methacrylic acid with alkanols containing 1-12, preferably 1-8, carbon atoms, such as, for example, methyl acrylate, acrylate, propylacetate, n-butyl acrylate, isobutylamine, 2-ethyl hexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butylmethacrylate, isobutylacetate.

These vinyl NITRILES containing from 3 to 12 carbon atoms. In particular, it Acrylonitrile and Methacrylonitrile.

Specified the styrene can be replaced completely and is about to carry out the copolymerization some of these main monomers with at least one other monomer or ethyleneamines connection taken in an amount of up to 40% by weight of the total weight of monomers selected from among the following compounds:

(e) vinyl esters of carboxylic acids such as vinyl acetate, vinylistic, finalproject,

(f) Ethylenediamine mono - and dicarboxylic acids, such as acrylic acid, methacrylic acid, taconova acid, maleic acid, fumaric acid,

(g) complex monoalkylated the above-mentioned dicarboxylic acids (f) with alkanols containing 1-4 carbon atoms and their N-substituted derivatives,

(h) amides of unsaturated carboxylic acids, such as acrylamide, methacrylamide, N-methylolacrylamide or N-methacrylamide,

(i) ethylene monomers containing a sulfonic acid group and its alkali or ammonium salts, such as, for example, vinylsulfonic acid, vinylbenzenesulfonic acid - acrylamidophenylboronic acid, 2-sulfoaildenafil,

(j) Ethylenediamine monomers containing a secondary, tertiary or Quaternary amino group or nitrogen-containing heterocyclic group, for example, vinylpyridine, vinylimidazole, aminoalkyl(meth)acrylates and aminoalkyl(meth)acrylamide, such as dimethylaminoethylacrylate or-methacry is zwitter-ionic monomers, such as sulfopropyl(dimethyl)aminopropylsilyl,

(k) esters of (meth)acrylic acid with arcangioli containing preferably 2-8 carbon atoms, such as mono(meth)acrylate glycol mono(meth)greatexample, mono(meth)acrylate 1-4 butanediol, and monomers containing two double polymerized communication, such as of ethylene glycol dimethacrylate.

In addition to the above monomers in paragraphs (e) through(k), can also be used, but in smaller quantities, comprising from 0.1 to 5 wt.% the total weight of the monomers, Ethylenediamine monomers which are capable by their nature be crosslinked, such as glycidyl(meth)acrylate (1) or vinyl or acrylic silanes (m), such as VINYLTRIMETHOXYSILANE and vinyltriethoxysilane.

In addition to the above monomers in paragraphs (e) through(m), can also be used in amounts up to 40 wt.% the total weight of the monomers or ethyleneimine compounds, functionalized polyorganosiloxane (n), having at least one ethylenediamino group (for example, vinyl or (meth)acrylic group) capable of reacting radical way with at least one of Ethylenediamine monomers (a) to(d) may, with at least one and what syruppy) (see in more detail in EP-0635526).

As a dispersion (B), may be used in the framework of the present invention can, in particular, called dispersion containing homopolymers derived from monomers (a), (c) and (e).

As latexes (B) copolymers can, in particular, to call latexes containing copolymers derived from:

- at least one monomer (a) at least one monomer (d) and at least one monomer (f),

- at least one monomer (a) and at least one monomer (c),

at least two monomers (c), of a different nature,

- at least one monomer (c) and at least one monomer (f),

- at least one monomer (c) at least one monomer (e) and at least one monomer (g),

- at least one monomer (c) and at least one monomer (e),

- at least one monomer (c) and at least one monomer (m).

In accordance with the above law of diffusion RELIGA, we can say that at any given silicon matrix light transmission elastomer containing polymer filler, according to the invention the polymer particles is Tomer, containing the same polymer filler, but consists of much larger particles, i.e. particles larger than 0.06 micron (60 nm). It can also be stated that, for a given particle size of the polymer light transmission filler elastomer always significantly improved by reducing the refractive index of the polymer forming the filler, i.e., improved by adequate changes in the chemical composition of the specified polymer.

According to a preferred variant implementation of the present invention, allowing to obtain an elastomer with adjustable light transmission in the range from medium to high values, use the latex (B) having the following characteristics:

- the size of the latex particles is from 0.01 μm (10 nm) to 0.08 μm (80 nm), preferably from 0.02 μm (20 nm) to 0.06 μm (60 nm),

the dry matter content is from 10 to 50% by weight.

According to another even more preferred variant of the invention, to achieve the desired light transmission use latex (B) having a particle size and dry matter content above, and containing the following acrylic (co)polymers:

- acrylic homopolymers, receiving the Bo of at least one monomer (c) and at least one other acrylic monomer, taken from the group of monomers (f), for example, (meth)acrylic acid, from the group of monomers (h), for example, acrylic derivatives, and from the group of monomers (k).

In the case of copolymers, partially derived from acrylic monomers (c), or (c) + (f) and/or (h) and/or (k) use of acrylic monomers in the amount of 70-99 wt.% the total weight of the monomers, and preferably in an amount of 80-99 wt.% the total weight of the monomers.

Of course, the mechanical properties of the latex (B) largely depend on the monomers selected for their manufacture. The polymers, which is part of the latex (B) may have a glass transition temperature Twithfrom -70oC to +230oC.

According to another even more preferred variant implementation of the present invention used in the process water dispersion (B) latexes are described above in the "preferred embodiment", in which the acrylic polymer components have a glass transition temperature Twithin the range from +50oC to +130oC. Skilful selection of these values of Twithcan provide a maximum hardening (i.e., best performance tensile strength).

The polymer constituting the latex (B), typically have an index of prelola the xiand represent the volume fraction and refractive index, respectively, of each component of the polymer (see the publication "Polymer Handbook", 1989, p. VI (452-461).

According to a particularly preferred variant implementation of the present invention used in the invention aqueous dispersions (B) latexes are as defined above in the description of option called "more preferred", and in which the refractive index polymer is in the range from of 1.34 to 1.50.

According to several excellent variant implementation of the invention in which get elastomer, adjustable light transmission of which is in the range of values that are significantly below the range of medium and high values of light transmission, as discussed above in the description of the preferred embodiments of the invention, use latex (B), which has the following characteristics:

this latex consists of particles, the size of which is enclosed in the range from values slightly in excess of 0.08 μm (80 nm) to 10 μm, and preferably from values slightly in excess of 0.08 μm (80 nm) to 2 μm, and the content of dry matter is equal to from 30 to 70 wt.%,

this latex contains AK is

According to yet another excellent and preferred version of the implementation of the present invention used in the process water dispersion (B) latexes are as defined above in the description of "good" option, and in which the acrylic polymer components have a glass transition temperature Twithfrom +50oC to +130oC.

And finally, according to another variant, referred to as "an excellent and preferred" used water dispersion (B) latexes are as defined above under option "a great and preferred and in which the refractive index polymer is in the range from of 1.34 to 1.50.

GETTING LATEX (B):

A person skilled in the art will be able to get the latex (B). There are several ways to obtain aqueous dispersions of organic polymers, namely:

through radical polymerization in emulsion,

by direct polymerization of the microemulsion of the corresponding(common) monomer(ROS),

- by emulsification and solvent evaporation: this method consists in dissolving the polymer in vodosmeshivayuschego solvent having a boiling point below the temperature which,

through deposition in Herstorical: this method is that the polymer is dissolved in a miscible with water, the solvent, after which the precipitated polymer in the water,

through KOATSERVATSII: this method consists in processing a homogeneous solution in order to cause phase separation with the formation of the colloidal phase (with a high content of polymer), varying physical parameters such as the pH or the temperature.

For the implementation of the present invention is preferred to obtain latex (B) is a method of radical polymerization in emulsion.

As for the latex (B) with a very fine particle size, i.e., from 0.01 μm (10 nm) to 0.08 μm (80 nm) used in preferred embodiments to implement the present invention, these latexes get the preferred radical polymerization method described in the patent EP-A-0644205 (cited as reference). According to this method, the monomer(s) portion is introduced into the aqueous reaction medium with simultaneous introduction (if necessary, also a La carte) initiator(ROS) free radicals.

THE CONNECTION OF THE METAL AS THE CURING CATALYST (C):

As for soedineniya. However, it is recommended to use the compound (C) in the framework of the present invention.

Catalytically active compounds of the metal (C) accelerating the curing process, are mainly salts of carboxylic acids and halides of such metals as lead, zinc, zirconium, titanium, iron, tin, barium, calcium and manganese.

Component (C) is preferably tin-containing catalytically active compound, usually an organic tin salt introduced into the process is preferably in the form of an aqueous emulsion. Suitable ORGANOTIN salts already described in the literature, in particular, in the publication NOLL, "Chemistry and Technology of Silicones", Academic Press (1968), p. 337. If necessary, such emulsions can be stabilized, for example, with polyvinyl alcohol.

You can also use the reaction product of alkylsilane or arietelloidea with diacetate dibutyrate (described in Belgium patent BE-A-842305).

For the present invention preferred are salts of tin: bischelate tin (patent EP-A-0147323 and EP-A-0235049), dicarboxylate georganopoulou, in particular, diversitate dibutil or dactylology (the United Kingdom patent GB-A-1289900), diacetate dibutil - or dictate from 0.01 to 3, preferably from 0.05 to 2 parts, per 100 parts of component (A1).

OTHER OPTIONAL ADDITIVES:

Aqueous dispersions according to the present invention may also contain one or more additives, namely:

(D): if necessary, the dispersion may contain from 0.1 to 20 parts by weight of the adhesive agent per 100 parts by weight of oil or polymer (A1),

(E): if necessary, the dispersion may contain from 0.1 to 5 parts by weight of nonionic, anionic or cationic silicone surfactants per 100 parts by weight of oil or polymer (A1),

(F): optionally, the dispersion may contain an effective amount of at least one compound selected from among anti-fungal, anti-foam or protivolistnyh substances, such as ethylene glycol and propylene glycol, as well as thixotropic agents, such as carboxymethylcellulose and xanthan gum.

Adhesive agent (D) is preferably chosen from among silicon compounds containing at the same time: (1) organic group, substituted by radicals selected from amino, ureido, isocyanate-, epoxy-, alkenyl, isocyanurate, hydantoin radical complex mercaptoethane and (2) idlebusy organosilicon compounds (D) shows the structural formulas (see at the end of the description) and with indication of the relevant patents.

Silicone surface-active compound (E) preferably chosen from the ranks of polyorganosiloxanes, which are functionalized in various ways, namely: or combinations of ethylene oxide or propylene oxide (a compound of the type commercially available on the market under the name TEGOPREN types 30, 58 or 70; it is issued by the company GOLDSCHMIDT, or converted into a salt with amino groups (the agent of this type is also present on the market under the name TEGOPREN type 69 company GOLDSCHMIDT), or metal sulphonate groups (see in this connection the author M. K. Sharma "Surface Phenomena and additives in water-based coatings and printing technology", Plenum Press, New York, pp. 73-82, this book describes the connections of the specified type).

OBTAINING A WATER DISPERSION ACCORDING TO THE PRESENT INVENTION

To produce aqueous dispersions according to the present invention, it is recommended to do the following: while stirring and at ambient temperature to the emulsion (A) adding a dispersion (B), then a metal curing catalyst (C), possibly in the form of a dispersion or emulsion of water and, if necessary, and optionally one or more additives (D), (E) and/or (F). When this mod is and dispersion (B).

The pH of the water dispersion may be acidic, neutral or basic. However, it is desirable to set the pH of the dispersion at a level greater than 7, preferably in the range from 8 to 13, with strong organic bases or preferably a strong mineral bases (such as triethanolamine or preferably caustic soda and caustic potash). Received thus prepared dispersion is homogenized, then Tegaserod and finally Packed in containers impermeable to oxygen and water vapor.

Components (A), (B), (C) and, optionally, (D), (E) and/or (F) are mixed in such quantities that the final emulsion had a dry matter content of at least 60%, preferably 80-95% by weight.

To determine the dry matter content, it is necessary to place a portion of 2 g of a dispersion in an aluminum crucible, and then the crucible is heated for 3 h at 50oC in an oven with circulating flow of dry air. After cooling, the crucible, it is again subjected to weighting and determine thus the percentage of substances remaining from the original two grams, i.e., get the value of the dry matter content.

According to prefer room temperature over a period of from several hours to several days. This operation maturation consists simply in the fact that the variance of leave without access of oxygen before subsequent use.

The dispersion according to the present invention can be used in the building materials industry to obtain translucent silicone elastomeric products, in particular sealing mastics, sealing putty, waterproof coatings, building facades, plaster and other materials for the facing surfaces exposed to the weather, and the dispersion is used in amounts of, for example, from 20 to 100 grams per square meter of treated surface.

The following examples illustrate the invention, not limiting the scope of its actions.

EXAMPLE 1 (comparative)

Prepare the emulsion (A), loading the bag mixer (manufacturer firm MEILI) with a capacity of 5 l of the following components:

- 1000 g- (dihydroxy)polydimethylsiloxane oil having a viscosity of 80,000 Masek at 25oC,

- 60 g gidroksilirovanii silicone resin containing 0.5 wt.% hydroxyl groups, consisting of 62 wt.% link CH3SiO1,5, 24% by weight of units (CH3)2SiO and 14% by weight of the attitude of CH3/Si = 1.5, the

45 g of surface-active nonionic agent GENAPOL X080, manufactured by HOECHST, which polyalkoxysiloxanes fatty alcohol containing 13 carbon atoms to about 8 parts of ethylene oxide, and

- 35 g of water.

The resulting mixture is subjected to homogenization within 180 minutes

Thus obtained emulsion (A) consists of particles with an average size of 0.5 μm (500 nm) and has a dry content to 96.9 wt.%.

In the same mixer to emulsion (A) is added with stirring for 10 min for each component the following components:

- water dispersion of precipitated CaCO3with a dry matter content of 43,6 weight. % consisting of 280 g CaCO3with an average particle size equal to 0.07 μm (70 nm) or the volume equivalent to the volume of the particles composing the boot polymer fillers according to further examples, and 13 g of dispersing agent in the form of an aqueous solution containing 40 wt.% polyacrylate sodium and 323 g of water,

- 10 g water emulsion containing 38 wt.% dilaurate di-n-Ochirova and stable 5 wt.% polyvinyl alcohol relative to the salt of tin, and

22 g of an aqueous solution of caustic potash, and the content of dry matter in the solution rawdata 81,3 wt.%.

After 4 days of storage make samples for subsequent measurements of various desired properties, namely:

THE MECHANICAL PROPERTIES OF TENSILE STRENGTH AND ELASTICITY

Using a scraper on a Teflon plate is applied film thickness of 2.5 mm, and then the film is dried for 7 days in an air-conditioned room (temperature 23oC 2oC, relative humidity 55% to 5%).

Sample H2, cut from the dried films are really measuring the following properties:

the elongation to break (AR %) and tensile strength (RR, MPa) according to the recommendations of the standard AFNOR-T-46002,

- elasticity (elasticity) (E,%) mastic by testing for relaxation under the following conditions: the sample is subjected to 100% final elongation at a speed of 300 mm/min, followed by relaxation of the elongated sample within 15 minutes the Value of the elasticity (elasticity) (in %) is calculated by the formula 100(1-C15/C0), in which C0and C15are the stresses experienced by the sample at the time of termination extension (C0and after 15 minutes the Size of the elasticity determine the average of 3 samples.

LIGHT TRANSMITTANCE (TRANSLUCENT)

Glass crucible depth 4 the air-conditioned room (temperature: 23oC 2oC, relative humidity 55% to 5%).

The light transmission of the sample is determined by the ratio of contrasts (contrast) (RC %) on the black and white background. This ratio is measured by the instrument DATACOLOR sold on the market the same company, under the following conditions: ambient light, the brightness value of the lighting C10when using a filter against UV rays and against the brightness. The amount of light transmission is estimated as the ratio of kontrastnosti RC = Y on a black background / Y on a white background 100%, in other words RC/100 is the ratio of the quantities Y (green light) tri-color coordinates of light reflected at an angle of 90 sample elastomer on a black and white background, respectively.

ADHESION

The amount of adhesion (A, in Newtons) of the elastomer is assessed through tests peeling (T) at an angle 180ofilm putty (putty) width 25 mm, deposited on a substrate of transparent glass. Peeling occurs at a rate of 50 mm/min, after 7 days of drying at the 23oC 2oC and at a relative humidity of 55% 5%.

Film putty (putty) reinforce the tape from the coarse polyamide fabric (type "Nylon 66"/ in the following way: first of all precipitated the first thick film is th silicone dispersion, in the result, get a sandwich type structure "mastic-polyamide-mastic".

The results of the measurements of all of these properties are given in table II.

EXAMPLES 2-7 (invention)

Proceed as described above in example No. 1, except that instead of a water dispersion of CaCO3use 330 g of the latex (B) having a fine particle size.

Characteristics of nanoliters used in examples 2-7 are shown in table I.

NOTES:

(1) MAM = methyl methacrylate, STY = styrene, ABu = butyl acrylate, MAA = methacrylic acid, VTEO = vinyltriethoxysilane.

(2) the Value of Twith- measured by the method of differential calorimetric analysis (it is described in the publication "Differential Scanning Calorimetry on DSC according to the recommendations of the standard AFNOR T 51-5077).

(3) refractive Index (co)polymer is calculated based on the refractive indices of the homopolymers according to the rule of additivity GLADSTONE-DALE, i.e. polystyrene = 1,591, acrylic polyacid = 1,527, methyl polymethacrylate = of 1.485, butyronitrile = 1,4666.

GENERAL GUIDELINES ON THE METHOD OF OBTAINING NANOLYTICS

Use a reactor with a capacity of 1 l stainless steel, equipped with stir bar and double administered 3 g of lauryl sodium, 240,3 g of water and 0.5 g of an aqueous solution containing 30 wt.% of ammonium persulfate. Next, the temperature of the contents of the reactor brought up to the 90oC, after which it is administered continuously for 2 h, 100 g of a mixture of Ethylenediamine monomers. In conclusion, the dispersion is cooled and filtered. The result is a latex grayish-blue color, having a solids content of 30 wt.% and the average particle size of 0.04 μm (40 nm). The dispersions obtained according to examples 2 to 7, have a pH of 12 and a solids content 81,3%.

Properties of elastomers reinforced with nanopaticle and properties of carbonate-bearing elastomer, taken for comparison in table II.

So, we can say that the elastomers reinforced with nanopaticle have properties comparable to the properties of the elastomer, reinforced with carbonate, and exceed these properties, while their light transmission is clearly higher.

1. Aqueous dispersion based on silicones and organic(fir) (co)polymer(s) which is capable of crosslinking by removing water by drying in ambient conditions with obtaining elastomer, having adjustable light transmission and superior mechanical properties, characterized in that pointed to by the oil-in-water, consisting of 100 weight.h. oil or ,-(dihydroxy)polydiorganosiloxane polymer (A1) and from 1 to 100 weight.h. organosilicon crosslinking agent (A2), stabilized by at least one surface-active agent (A3) selected from anionic and non-ionic surface-active compounds and mixtures thereof with a particle size of from 0.1 μm (100 nm) to 100 micrometers (100000 nm) with a dry matter content of at least 60 wt.%; (C) 1 to 100 weight.h. aqueous dispersions of at least one organic (co)polymer per 100 weight.h. oil or polymer (A1) and a specified organic (co)polymer has a particle size of from 0.01 μm (10 nm) to 10 microns (10 000 nm), the dry matter content of 10 to 70 wt.%; (C) optionally, from 0.01 to 5.0 weight.h. the catalytically active metal compounds that contribute to curing, on

100 weight. including oil or polymer (A1), and the specified aqueous dispersion has a dry matter content of at least 60 wt.%; regulation of the quantity of light transmission of the formed elastomeric product is at the stage of obtaining this water dispersion by adjusting to the desired(appropriate) value(s) of the following options: either the particle size of the polymer latex (B), or the refractive index pakazanych parameter, i.e., the particle size and refractive index simultaneously.

2. Dispersion under item 1, characterized in that ,-(dihydroxy)polydiorganosiloxane (A1) has a viscosity of at least 50 000 MPa s at 25oC, and the organic radicals of these siloxanes are monovalent hydrocarbon radicals containing up to 6 carbon atoms and optionally substituted by cyano groups or fluorescent.

3. Dispersion under item 1 or 2, characterized in that the crosslinking agent (A2) selected from the group of the organosilicon compound of the microemulsion type resin silsequioxane resin, a reactive silicone resin having a low molecular weight and containing alkoxy - and alloctype, high molecular weight silicone resin, insoluble in toluene, gidrauxilirovannaya silicone resin, the molecule of which contains at least two different element selected from R3SiO0,5(M), R2SiO (D), RSiO1,5(T), and SiO2(Q) where R is mainly C1-6the alkyl, vinyl, trifter-3,3,3-propylene and in which the weight content of hydroxyl groups is 0.1 to 10.0%, silanes of the formula RaSiX4-ain which R is a monovalent organic radical, in particular methanol preferably from among the groups of alkoxy, acyloxy, climinax, alkylamino, amido, alkenylacyl and their various mixtures.

4. Dispersion according to any one of paragraphs.1 to 3, characterized in that the aqueous dispersion (A) contains organic (co)polymers, which are the (co)polymerization of at least one main monomer, selected from among the following compounds: styrene (a), butadiene (b), a complex of acrylic esters and vinyl NITRILES (d), and some of these main monomers (a) to (d) can copolymerisate with at least one other monomer in a quantity of up to 40% of the total weight of monomers, or with an unsaturated compound selected from among (e) vinyl esters of carboxylic acids, (f) Ethylenediamine mono - and dicarboxylic xilu, (q) complex monoalkylation these dicarboxylic acids under paragraph (f) with alkanols containing 1 to 4 carbon atoms and their N-substituted derivatives, (h) amides of unsaturated carboxylic acids, (i) ethylene monomers containing sulfonic acid group, and sulfonic acid salts of alkali metals or ammonium, (j) Ethylenediamine monomers containing a secondary, tertiary or Quaternary amino group or anotadoras Iolani, containing preferably 2 to 8 carbon atoms, and monomers containing two double polymerized communication, (l) methacrylate of glycidyl, (m) vinyl or acrylic silanes, (n) functionalized polyorganosiloxanes containing at least one ethylenediamino group that can react with other ethyleneamines monomer by a radical mechanism.

5. Dispersion according to any one of paragraphs.1 to 4, characterized in that, for obtaining an elastomer, having adjustable light transmission in the range from medium to high values, use the latex (B) having a particle size of from 0.01 μm (10 nm) to 0.08 μm (80 nm) and the dry matter content of 10 to 50 wt.%.

6. Dispersion under item 5, characterized in that the aqueous dispersion or latex (B) include acrylic homopolymers derived from monomer (C), and copolymers obtained wholly or partly either from acrylic monomers (C), or from at least one monomer (C) and at least one other acrylic monomer taken from the monomers of group (f), used as the (meth)acrylic acid monomers of group (h), is used as the acrylic derivatives and of monomers of groups (k), moreover, when copoly the SJ-70 - 99% of the total weight of the monomers.

7. The variance in p. 6, characterized in that the aqueous dispersion (A) contains organic acrylic (co)polymers having a glass transition temperature Twith= 50 - 130oC.

8. Dispersion under item 7, characterized in that the aqueous dispersion (A) contains organic acrylic (co)polymers with Twith= 50 - 130oC, and the refractive index n = 1,34 of 1.50.

9. Dispersion according to any one of paragraphs.1 to 3, characterized in that, for obtaining an elastomer with adjustable light transmission in the range of magnitude below the values range from medium to high on p. 5, use latex (B) having a particle size of from values slightly in excess of 0.08 μm (80 nm), up to 10 μm and the dry matter content of 30 to 70 wt.%, and containing the acrylic (co)polymers under item 6.

10. Dispersion under item 9, characterized in that the aqueous dispersion (A) contains organic acrylic (co)polymers with a glass transition temperature Twith= 50 - 130oC.

11. Dispersion under item 10, characterized in that the aqueous dispersion (A) contains organic acrylic (co)polymers with Twith= 50 - 130oC and the refractive index n = 1,34 of 1.50.

12. Dispersion according to any one of paragraphs.5 - 8, otlichayas is from PP.9 - 11, characterized in that the latex (B) has a particle size of from values slightly in excess of 0.08 μm (80 nm), up to 2 ám.

14. Dispersion according to any one of paragraphs.1 - 13, characterized in that the emulsion (A) has a dry matter content of 80 to 98 wt.%, the final aqueous dispersion has a dry matter content of 80 to 95 wt.%.

15. Dispersion according to any one of paragraphs.1 to 14, characterized in that the metal compound (C) is an ORGANOTIN salt in the form of an aqueous emulsion.

16. Dispersion according to any one of paragraphs.1 - 15, characterized in that it is intended to obtain a translucent silicone elastomer products in the form of sealing and sealing mastics and putties, llers and protective coatings for facades of buildings in the construction industry.

17. A method of obtaining a water dispersion in PP.1 - 15, characterized in that at ambient temperature to the emulsion (A) first add the dispersion (B), then a metal curing catalyst (C), possibly in the form of a water dispersion or emulsion, and then, perhaps, introduce additive(s).

18. The method according to p. 17, characterized in that the pH of the final aqueous dispersion is set at the level above 7 by adding a strong mineral base

 

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