Polymer composite and method thereof

 

The invention relates to polymeric composites (options), the way they are received and equipped with the fiber composite. The polymer composite includes a matrix representing epoxygenase ester resin and dispersed therein capable of swelling the layered inorganic material having organophilicity properties due to embedded organic material layer. In the second variant of the composite matrix is epoxygenase ester resin or unsaturated complex polyester or mixtures thereof, and inorganic material has organophilicity properties due to embedded material layer is 27% of the variance clay hectorite in propylene glycol. The invention allows to obtain nanocomposites with improved physico-mechanical properties: heat resistance, chemical resistance, rigidity. 4 N. and 17 C.p. f-crystals, 1 tab., 8 Il.

This invention relates to a polymer composite that includes a polymer and an inorganic additive, more specifically, the layers are able to swell the material, and to a method for producing a polymer composite.

Polymer composites comprising a polymer matrix with one or more Debevoise, well known. Supplement is often injected to improve one or more properties of the polymer.

Usable additives include inorganic layered materials, such as talc, smetana clay and mica micron size. These materials also can be called inorganic silicates. You can also use other inorganic layered materials, not containing silicon.

A number of techniques describes the dispersion of the inorganic layered material in a polymer matrix. It was suggested atomized individual layers, for example plates, layered inorganic material throughout the polymer. However, without some additional processing of the polymer will not leak into the space between the layers of the additive in sufficient quantity and layers of the inorganic layered material will not be sufficiently uniformly dispersed in the polymer.

As described in U.S. patent 4889885, more homogeneous dispersion of the layered inorganic material in the polymer facilitates the exchange of sodium and potassium ions normally present in natural forms of inorganic silicate or silicates of the type of mica or other multilayer microtrenching materials on onevia ions (for example, the first currency can pay normally hydrophilic silicate type mica in organohalide and to extend the distance between layers of the layered material. An additional method of treatment of the silicate type mica in organohalide is the dispersion or the synthesis of glycol or other suitable solvent. Organohalide silicates type mica include such materials which are commonly referred to organogram. Hydrophilic silicate type mica in organophilic you can pay in other ways. Subsequently, the layered material (commonly called "nannapaneni") is mixed with the monomer and/or oligomer of the polymer and the monomer or oligomer will polimerizuet. Nannapaneni can also be mixed or compounded with the polymer in the melt. The mixing of the nanofiller with the monomer, oligomer or polymer leads to an increase in the average interlayer distance of the layered material. This increase in the average space between the layers is called delamination or exfoliation of the layered material.

In WO 93/11190 described an alternative method of obtaining a polymer composite in which the layered material in the form of particles having reactive organosilane compounds dispersed in a thermoplastic polymer or vulcanizing the rubber.

In addition, additional polymer composites containing these so-called nannapaneni and/or SPO is 474 and 1719-1725; and Vol. 7 S. 2144-2150; and Chem. Mater. Vol. 8, S. 1584-1587 (1996).

In U.S. patent 5554670 described transverse cross-linked nanocomposites based on epoxides derived from simple diglycidylether ether of bisphenol A (DGEBA) and certain specific vulcanizing agents. This patent States that a bifunctional primary or secondary amines do not give a layered nanocomposite structure, but instead lead to the formation of opaque composites.

Chem. Mater. Vol. 8, S. 1584-1587 (1996) reveals the importance of the full ion exchange in the formation of organogels to obtain nanocomposites with maximized performance.

However, even despite these numerous described composites and methods, it still remains desirable to have an improved method of making polymer composites using multi-layer additives for composites with improved properties in comparison with a single polymer.

Accordingly, in one aspect of the present invention is a polymer composite comprising a matrix of epoxyphenolic ester resin, unsaturated complex polyester or mixtures thereof, containing buried in her layered or debonded particles formed of multi-stakeholder the invention is a method of producing composite, which includes interaction epoxygenase ester resin, unsaturated polyester, or a mixture thereof with a layered inorganic material that has organophilicity properties.

Polymer composites of the present invention can show an excellent combination of properties and can demonstrate one or more superior properties such as improved heat resistance or chemical resistance, impedance fire, slow burning, excellent resistance to diffusion of polar liquids and gases, the yield strength in the presence of such polar solvents as water, methanol or ethanol, or increased rigidity and dimensional stability compared to composites that contain the same layered inorganic material that is not attached to organophilicity.

Polymer composites of the present invention can be used as release films, the separating pins or other molded or extruded products made of thermosetting plastic, using any traditional methods of production of thermosetting plastics. Such products can find a wide variety of applications, including such infrastructure is tov), in electronics, office equipment, for example, for a computer case, in the production of construction materials and packaging materials.

Fig.1 - radiograph (x-ray diffraction) unsaturated complex polyester composite described in example 1.

Fig.2 - radiograph of unsaturated complex polyester composite described in example 2.

Fig.3 - radiograph of a composite material based on vinyl ether complex described in example 3 to curing.

Fig.4 - radiograph of a composite material based on vinyl ether complex after curing the cobalt naphthenate described in example 3.

Fig.5 is an electron microscopic picture of a composite based on vinyl ether complex, shown in Fig.4, which was overiden the cobalt naphthenate and MACR (methyl ethyl ketone peroxide), obtained with a transmission electron microscope at 300-fold increase.

Fig.6 - radiograph of a composite material based on vinyl ether complex after curing peroxide benzoyl (VRO) and N,N-dimethylaniline (DMA), described in example 3.

Fig.7 - electron microscopic picture of a composite based on vinyl ether complex, shown in Fig.5 and described in example 3, which is enterographa composite based on vinyl ether complex obtained by the addition of clay In after the synthesis of vinyl ether complex described in example 3.

In the present invention the polymer matrix of the polymer composite comprises a resin-based epoxiconazole of ester or unsaturated complex polyester or a mixture thereof.

Resin-based complex epoxiconazole ether, which can be used in the implementation of the present invention to obtain a polymer composite described in concurrently pending application No. 382,028, filed February 10, 1995. In General, these resins based epoxiconazole of ester can be obtained: (1) the interaction of polyepoxide with ethyleneamines carboxylic acid to obtain a reaction product, which partially contains C(=O)-O-CH2-CH2IT is a functional group formed by the interaction of epoxy groups with carboxyl acid group, or (2) subsequent condensation of secondary hydroxyl groups contained in the above-described product of the reaction, the anhydride Dwuosobowy carbonneau acid with the formation of lateral polovinych groups. The resulting resin-based epoxiconazole of ester then Ene resin polyepoxide preferably added in a quantity sufficient to provide from 0.9 to 1.2 equivalents of epoxide per equivalent of carboxylic acid. If desired, further condensation of secondary hydroxyl groups complete the addition of the anhydride of dicarboxylic acid with obtaining side polovinych groups with a secondary alcohol group resulting from the reaction of epoxide and carboxylic acid. The dosage of this added anhydride of dicarboxylic acids can be changed to turn part or all of the secondary hydroxyl group in the side polovinye group.

Ethylenediamine carboxylic acids which are preferred for the reaction with polyepoxides include,unsaturated monobasic carboxylic acid and a complex palefire based duotronic carboxylic acids and hydroxyalkyl acrylate or methacrylate.,Unsaturated monobasic carboxylic acids include such acids as acrylic acid, methacrylic acid, crotonic acid and cinnamic acid. Hydroxyalkyl acrylate group or methacrylate complex profirov preferably contains from two to six carbon atoms and may be, for example, hydroc the oxygen simple ether. Guenoune carboxylic acid by nature can be either saturated or unsaturated. Saturated acids include phthalic acid, chlorendic acid, tetrabromophthalic acid, adipic acid, succinic acid and glutaric acid. Unsaturated guenoune carboxylic acid include maleic acid, fumaric acid, citraconate acid, taconova acid, halogenated maleic or fumaric acid and metaconule acid. You can use a mixture of saturated and Ethylenediamine duotronic carboxylic acids.

Preferably used palefire get the interaction of essentially equimolar amounts of hydroxyethylacrylate or methacrylate anhydride with Dwuosobowy carboxylic acid. Other unsaturated anhydrides that can be used include maleic anhydride, citraconic anhydride and itacademy anhydride. Preferred saturated anhydrides that can be used include phthalic anhydride, tetrabromophthalic anhydride and the anhydride florentikoli acid. Mostly, when receiving profirov use of polymerization inhibitors such as hydroquinone or a simple methyl ether of hydroquinone.

For receiving titlename polyepoxide are simple glycidyloxy polyether polyols, polyhydric phenols, epoxydodecane, epoxide modified elastomer, halogenated epoxides, epoxydecane fatty acids or drying oil acids, epoxydecane diolefine, amoxicilline esters dunension acid, epoxydecane unsaturated polyesters, and mixtures thereof, as they contain more than one epoxy group per molecule. Polyepoxide may be in the nature of a Monomeric or polymeric. Preferred polyepoxide include polyethers of glycidyl and polyhydric alcohols or polyhydric phenols having a weight per epoxy group (EEW) of from 150 to 2,000. Such polyepoxide usually be obtained by interaction between at least two moles of epichlorhydrin or dehalogenation of glycerol with one mol of a polyhydric phenol and sufficient for connection of halogen gelegenheden amount of caustic soda. These products are characterized by on average one epoxy group per mole, that is, 1,2-epoxy equivalence greater than unity.

Preferred anhydrides of dicarboxylic acids for reaction with the secondary hydroxyl groups include saturated anhydrides, such as phthalic anhydride, tetrabromophthalic angiedenni dicarboxylic acids, such as maleic anhydride, the anhydride tarakanovas acid and anhydride basis of itaconic acid.

Polimerizacionnye monomer can be any monomer that is polymerized with epoxygenase complex ester resins or polyester resins. Preferably, when poliarizatsionnoy monomer includes ethylene unsaturation. A wide selection of polimerizatsionnyh monomers containing >C=CH2group, available from many well-known classes of vinyl monomers. Preferred polimerizacionnye monomers are styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, Orta-, meta - and para-halogenation, vinyl naphthalene, the various alpha-substituted styrene, and various di-, tri - and Tetra-halogenation and acrylic esters of methacrylic and crotonic acids include esters of saturated alcohols, and esters of hydroxyalkyl or mixtures thereof. Styrene is the preferred copolymerization monomer. Usually poliarizatsionnoy monomer is present in amounts lying in the range from 20 to 60 weight percent of the composition based on complex vinylester resin, depending on the desired con the market and catalysts. You can use any well-known inhibitors of vinyl polymerization, such as hydroquinone or a simple methyl ether of hydroquinone. In addition, the reaction polyepoxide with carboxylic acid can be carried out either in the presence or in the absence of a catalyst, such as an alcoholate and tertiary aminophenols.

Preferred epoxygenase complex essential oils that can be used in the practice of the present invention when receiving a polymer composite, the ones that are supplied by Dow Chemical Company under the trademark DERAKANE. A particularly preferred resin is a General purpose, known as resin-based complex epoxiconazole ester DERAKANE 411-45, which contains approximately 45% Monomeric styrene. Other resin-based complex epoxyphenolic esters brand DERAKANE that can be used include, for example, resin-based complex epoxiconazole ester DERAKANE 411-C-50, containing approximately 50% Monomeric styrene; resin based on complex epoxiconazole ester DERAKANE 470-36 containing approximately 36% Monomeric styrene; resin based on complex epoxiconazole ester DERAKANE 470-30 containing approximately 30% Monomeric styrene; resin-based complex epoxyphenol the additional 40% Monomeric styrene; resin-based complex epoxiconazole ester DERAKANE 790, containing approximately 45 percent Monomeric styrene; and resin-based complex epoxiconazole ester DERAKANE 8084, fluidized resin based on complex epoxiconazole ether containing approximately 40% Monomeric styrene.

Well-known unsaturated polyesters that can be used in the practice of the present invention. They contain carboxyl complex ester group and a carbon-carbon double bond as alternating units of the main polymer chain. They are usually obtained by condensation of (a) Ethylenediamine dicarboxylic or polycarboxylic acids or anhydrides, for the introduction of unsaturation, (b) saturated dicarboxylic acids for modification of the resin, and (C) diols or polyols. Unsaturated polyester resins have the General structural formula of:

(R-O-C(=O)-R'-C(=O)-O)x(R-O-C(=O)-CH=CH-C(=O)-O)y

in which R and R' radicals of alkylene or arylene in diola and a saturated acid, respectively, and x and y are variables, which depend on the composition and conditions of condensation.

Typical di - or polycarboxylic acids or their anhydrides used to obtain the unsaturated polyesters include phthalic acid, ISO - or tieslau, citraconate acid, chlormadinone acid, allinternal acid, taconova acid, metaconule acid, citric acid, pyromellitic acid, timesyou acid, tetrahydrophthalic acid, thiodiglycolic acid. These acids and anhydrides can be used independently or together.

Typical di - or polybasic compounds used in the preparation of unsaturated polyesters include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropyleneglycol, glycerol, 2-butene-1,4-diol, hydrogenated bisphenol a, listenerdatatype simple ether, biphenyldicarboxylic simple ether and neopentylglycol.

To unsaturated complex polyesters to reduce their viscosity and to obtain a thermosetting product, you can add various reactive diluents or monomers. Typically, reactive diluents or monomers are used in amounts of from 10 to 25 weight parts, preferably from 10 to 20 weight parts per 100 weight parts calculated on the total weight of the curable composition, excluding the weight of any reinforcing particles present in the composition. Typical examples of such reactive monomers include styro is, lesterol, Olivenza; unsaturated esters, such as methyl methacrylate, methyl acrylate and other lower alifaticheskie esters of acrylic and methacrylic acids; allyl acetate, diallyl phthalate, diallyl succinate, diallyl adipate, diallyl sebacina, diethylene glycol bis(allyl carbonate), triethylphosphate and diethylene glycol bis(allyl carbonate); triethylphosphate and other allyl esters; and vinyltoluene, diallylmalonate, cialistadalafilat, ethylene glycosidically; and amides, such as acrylamide; vinyl chloride and mixtures thereof. From these examples, preferred is styrene.

The resins based on unsaturated complex epoxyphenolic polyesters or mixtures or other mixtures in which at least one component is a resin based on an unsaturated polyester or complex epoxiconazole ether, you can also add the curing agent. Examples of such curing catalysts include free radical initiators such as azo compounds, including azoisobutyronitrile, and organic peroxides, such as tert-butyl, perbenzoate, tert-butyl, peroctoate, benzoyl peroxide; methyl ethyl ketone peroxide, peroxide acetoacetate, cumene hydroperoxide, hydropel. Preferably, when the catalyst in an amount of from 0.03 to 2.5 parts by weight, calculated on the total weight utverzhdenii composition, excluding the weight of any reinforcing particles present in the composition.

Layered inorganic materials, which can be used in the implementation of the present invention to obtain polymer composites are any capable of swelling the layered inorganic materials. Usually layered inorganic material contains layers having two opposite surfaces, which can be relatively flat or slightly curved. Such materials are described in U.S. patent 4,889,885.

Illustrative examples capable of swelling the layered inorganic materials used in the implementation of the present invention include inorganic layered silicates, such as metribolone, nontronite, beidellite, volkonskoit, hectorite, saponite, sauquoit, MEGADETH, memetic, ceniai and vermiculite. When implementing the present invention can also be used for other laminates or multilayer aggregates having a small charge or no charge on the surface of the layer, provided that they can characterial, having charge more than the above-cited materials, such as members of the mica family, can also be used when implementing the present invention, provided that they can alternate layers with swelling agents, which expand their interlayer space can be used mixtures of one or more of such materials.

More typical examples of layered materials include elitnye minerals, such as sedikit; layered double hydroxides or mixed metal hydroxides, such as MD6Al3.4(OH)18.8(CO3)1.7H2O (see W. T. Reichle, J. Catal., 94 (1985), 547), which have positively charged layers and capable of ion exchange of the anions in the interlayer space; chlorides such as Rl3and FeOCl, chalcogenides, such as TiS2, MoS2; and S3; cyanides such as Ni(JV)2; and oxides such as H2Si2O5V5O13, HTiNbO5, Cr0.5V0.5S2, W0.2V2.8O7, CR3About8Moo3(OH)2, VO42H2Oh, Saro4CH3H2Oh, MnHAsO4H2O and Hell6Preferred are able to swell layered inorganic materials that can be used in the practice of the present invention to obtain a polymer composite, are those that have the charge on the layers and capable of exchanging ions, such as cations of sodium, potassium and calcium, which can be exchanged preferably by ion exchange, ions, preferably onevia ions, such as ammonium cations, or reactive compounds of organosilane that cause peeling or swelling of the layered particles. Usually the negative charge on the surface is able to swell the layered inorganic material is at least 20 milliequivalents, preferably at least 50 milliequivalents, and more preferably from 50 to 150 milliequivalents, 100 grams of layered material. Especially preferred are inorganic layered silicates such as montmorillonite, nontronite, beidellite, volkon is about 150 milliequivalents per 100 grams of material. Preferred are able to swell layered inorganic materials are inorganic layered silicates having a negative charge on the layers ranging from 0.2 to 1.2 charges at the molecular unit, the most preferred inorganic layered silicates having a negative charge on the layers ranging from 0.2 to 0.9 charges at the molecular unit, and is proportional to the number of the incoming ion exchange of cations in the interlayer spaces.

Capable of swelling the layered inorganic materials can be turned into organohalide a process known as "introduction", which includes the introduction of material layers (neutral or charged fragments) in the interlayer or mifepristone space capable of swelling the layered inorganic material, or by incorporating in the case of neutral molecules or ion exchange in the case of ions. The introduction of the interlayer may also increase the interlayer space capable of swelling the layered inorganic material. The term "interlayer or lifebalance space or distance" means the distance between the surfaces of the layers or the distance between the fibrils. In the case of ions ions can share more on the e any described layered material containing neutral or charged fragments in the interlayer region, which lead to the increase of the distance between the layers before the formation of the composite, will be called the material with the introduction or inorganic silicate with implementation. This description also includes such layered materials or inorganic silicates, which turned into organohalide. Such materials are usually known as organogeny.

The materials of the interlayer weaken the energy of cohesion between the layers due to swelling in the interlayer spaces and increase the compatibility and link layers with a polymeric matrix, with the ability to interact on the mechanism of attraction as with layers and polymer. The interlayer materials that swell in the interlayer or mifepriston space, hereinafter referred to as "swelling agents", those that increase the compatibility and link layers and fibrils of the polymer, referred to as "agents that improves the compatibility, and those who act as swelling agents and agents that improves the compatibility, referred to as "agents swelling/combine".

The interlayer materials can be introduced into the space between each layer or fiber, almost each layer or fiber capable of mterial layer in the interlayer region, capable of swelling the layered materials known to experts in the field of technology. See, for example, U.S. patent 4889885 Usuki, etc. does Not mean that these methods are limited to any particular process or procedure.

Material layer, as a rule, contain a functional group that interacts with the surface layers of the layered material and fully or partially replaces the original ions and binds to the surface layers. These functional groups that are reactive with respect to the polymer, include nucleophilic or electrophilic functional groups that can participate in reactions of electrophilic or nucleophilic substitution reactions combination and the various reactions to the disclosure of the ring. Examples of such functional groups include amino, carboxy, allalone, alkoxy, hydroxy, ureido isocyanate, halogen, epoxy, and epichlorohydrin.

Characteristically, the material layer also include a functional group in which the energy of cohesion is sufficiently similar to that of the polymer, so that the surface layer becomes more compatible, at least one polymer, thereby increasing the homogeneity of the variance in Y polymer matrix and a layered material conducive to accelerating the mixing of the polymer matrix and the layered material. Compatibility is determined by one or more of the following criteria: close values of the energy densities cohesion of polymer and type of particles, similar or complementary abilities to the dispersion, polar interactions and the formation of hydrogen-bonds, or other specific interactions, such as interactions of type of acid/base or Lewis acid/Lewis base. Increase compatibility can lead to improvements in plate dispersive ability of the pigment particles in the matrix and increase the percentage of stratified (or debonded) plates. The increase in the dispersion results in an increase in the average value of the interlayer space of the layered material in comparison with the magnitude of the initial interlayer space of inorganic silicate with an introduction to its contact with the polymer matrix.

The interlayer materials that can be used in the practice of the present invention include water-soluble polymers, onevia compounds such as ammonium salts, phosphonium or sulfone, amphoteric surface-active compounds, the compounds choline and organosilanols the invention, the interlayer, are water-soluble vinyl alcohol polymers, such as poly(vinyl alcohol); polyalkylene glycols such as polyethylene glycol; water-soluble cellulose polymers such as methyl cellulose or carboxymethyl cellulose; polymers Ethylenediamine carboxylic acids, such as poly(acrylic acid) and their salts; and polyvinylpyrrolidone. You can use the monomer units of these polymers, for example ethylene glycol or a mixture of ethylene glycol and propylene glycol, or propylene glycol.

Typical examples niewyk compounds that can be used as an organic layer in the practice of the present invention include cationic surfactants such as Quaternary ammonium salt containing octadecyl, hexadecimally, tetradecyl or dodecylphenyl fragments; with the preferred Quaternary ammonium salts, including octadecyl trimethyl ammonium salt, dioctadecyl dimethyl ammonium salt, hexadecyl trimethyl ammonium salt, dihexadecyl dimethyl ammonium salt, tetradecyl trimethyl ammonium salt, ditetradecyl dimethyl ammonium salt, dihydroxyethyl methyloctadecane ammonium salt, dihydroxyethyl methyl gidrirovannoe fatty arenovich segments, and salt polyoxyalkylene polyamines, such as JEFFAMINEproducts Huntsman Corp.

Typical examples of amphoteric surface-active agents that can be used as the organic material layers in the practice of this invention include surfactants having a cationic portion on the basis of aliphatic amine and carboxyl, sulfate, sulfonic or phosphate group as the anionic part.

Typical examples of the compounds choline, which can be used as the organic material layers in the practice of this invention include [NON2CH2N(CH3)3]+HE-, C5H14ClNO,5H14PIC4H5O6With5H14PIC6H7O7and C5H14PIC6H12O7.

Typical examples organosilane compounds that can be used as the organic material layers in the practice of this invention include silane agents of the formula:

(-)nSiR(4-n-m)R1m,

where (-) represents a covalent bond with the surface of the layered material, m=0, 1, or 2; n=1, 2, or 3, provided that the sum of m and n is equal to 3; Rthe l and alkoxyaryl) and not replaced during the formation of the composite; R is the same or different values in each case and represents an organic radical, which is not hydrolyzed and not replaced during the formation of the composite, which is chemically active with respect to the polymeric matrix or at least one monomer component of the polymer. Typical R groups include amino, carboxy, allalone, acyloxy, hydroxy, ureidosuccinate, halogen, epoxy and epichlorhydrin. Preferred organosilane interlayer materials include long chain branched Quaternary ammonium salt and/or organosilane connection with suitable Funktsionalnyi groups, as described in WO 93/11190, S. 9-21.

Organic materials other than those described can also be used as the organic material layers provided that they can be embedded between layers of the multilayer material of the microparticles.

Preferably, when the layered material with the implementation of the present invention is a silicate with the introduction of a layer thickness of from 7 to 12. This thickness of the layer does not include the thickness of the part with the material layer. The polymer composite of the present invention can be obtained from the multi-layered material with the procedure of polymeric composites.

In cases where a multilayer material with implementation and/or vinyl ester or unsaturated complex polyester are solids or viscous liquids, it is useful to use an inert solvent or diluent. Such suitable inert solvents or diluents known in the art the art and include ketones, such as acetone, methyl ethyl ketone, or hydrocarbons, such as benzene, toluene, xylene and cyclohexane.

Usually the solvent is left in the product, when receiving polymer composite using solvents and the final product will be used for coatings. Otherwise, the solvent is removed by some suitable means, such as distillation.

Layered material with the introduction may be dispersed in the monomer (monomers), which forms the polymer matrix and the monomer (monomers) will polimerizuet in situ, or Vice versa, it can be dispersed in a vinyl ether complex or unsaturated complex polyester or mixtures thereof, in the melt or liquid form.

Liquid or melt vinyl ether complex or unsaturated complex polyester containing layered material of the microparticles with the implementation, you can also recycle method is comfort in liquid or solid monomer or vulcanised agent, which forms or will be used for obtaining the polymer matrix of the composite. This dispersion can be injected into the melt polymer containing one or more polymers in the extruder or other mixing equipment. The injected fluid can lead to the formation of a new polymer or extending the chain of the graft copolymerization or even cross-linking of the polymer, which is initially in the melt.

As in the reactor the process of mixing, and the process of mixing in the melt, suitable for use layered and fibrous inorganic materials are preferably those which have been subjected to swelling and/or implementation organophilic interlayers between the layers or fibrils.

Methods of obtaining a polymer composite using in situ type of polymerization, also known and are referenced to explain the beings of the present invention. Applying this method in the implementation of the present invention, the composite is obtained by mixing the monomers and/or oligomers with a layered material in the presence or in the absence of solvent, followed by polymerization of the monomer and/or oligomers and the formation matrix composite based on complex vinyl afobam.

It is believed that such a multilayer material with the introduction favorably dispersed in the conditions, when at least about 50, preferably at least about 70, more preferably at least about 80, and most preferably at least about 90 weight percent of the layers of the multilayer material with introduction, present in the polymer composite has a larger interlayer space than inorganic silicate or inorganic aluminate prior to its introduction into the polymer matrix. It is likely that the layers of filler will be dispergirujutsja or delaminate in the polymer is not completely, but will form layers in co-planar Assembly. These layers are mainly dispersed or stratified in a polymer matrix to a sufficient extent, so that a significant portion of the layers has the interlayer space of more than 30preferably 50. Preferably, at least 50% of the layers had such space between the layers, more preferably more than 70% of the interlayer space was more than 50.

The sizes of the dispersed stratified layers can significantly izmenenii, rounded, elliptical or rectangular with a maximum diameter or length from 50 to 50000. The shape factor as such is a value between 5 and 5000, with the assumption that the typical thickness of the layer is about 10. The shape factor, which is most favorable to use will depend on the desired final properties. The surface of the particles can also be needle-like.

Optional polymer composites of the present invention may contain various other additives, such as agents, nucleation of crystals, other fillers, softeners, plasticizers, extenders circuits, dyes, agents that facilitate the seizure of articles from molds, antistatic agents, pigments or flame retardants.

Optional additives and their amounts used, depending on various factors, including the desired final properties.

Polymer composites of the present invention possess valuable properties. For example, they may have an increased yield strength and modulus of tensile elasticity, even when exposed to a polar environment such as water or methanol; increased resistance to heat and shock and reduced absorption of moisture, Flammability and permeability compared with the same polymers that contain the same multilayer material, which previously did not contain implementation or which did not use the material layers. Improving one or more properties can be obtained even when using small amounts of layered materials with implementation.

Polymer composites of the present invention can be molded conventional profiling methods, such as forming from the melt, casting, vacuum molding, film molding, injection molding and extrusion, blown melt spinning, pneumotropica, and co - or multi-layer extrusion. Examples of such handicap products include components for technical equipment, hardware casting, equipment for household, sports equipment, bottles, containers, products for energy and electronic industries, automotive parts and fibers, the use of such infrastructure as roads and bridges, the application of marine coatings. Composites can also be used for products with a coating of powder or as glues melt.

Polymer composites of this isoperimetry. Conversely, it is also possible to obtain a molded product by conducting the polymerization reaction in situ in the mold.

Polymer composites in accordance with the invention is also suitable for the production of sheets and panels using such conventional processes such as vacuum or hot pressing. The sheets and panels can be laminated with materials such as wood, glass, ceramics, metal or other plastics, and very high strength can be achieved through the use of conventional adhesion promoters, for example, vinyl-based resins. The sheets and panels can also be laminated with other plastic films using the extrusion method, sheets, United in the molten state. Surfaces for finishing sheets and panels can be accomplished by known methods, for example, by coating or applying protective films.

Polymer composites of the present invention can also be used for the production of extruded films and film laminates. Such films can be produced by known extrusion technique films. Film thickness is preferably from 10 to 100, more preferably from 20 to 100, and most preferably from 25 to 75 microns.

Polymer HDMI in which the polymer matrix is reinforced by one or more reinforcing materials, such as a reinforcing fiber or frame. Fiber, which can be used in the method of the present invention, are described in numerous references, such as, for example, U.S. patent. 4533693; Kirk-Othmer Ency. Chem. Tech., Aramid Fibers, 213 (J. Wiley & Sons 1978); Kirk-Othmer Ency. Chem. Tech. - Supp., Composites. High Perfomance, pages 261-263; Ency. Poly Sci & Eng. Fiber can be different in composition, provided that they do not melt in the process of obtaining composite, and mostly they are chosen so that these fibers provide improved physical properties, such as limit values of tensile strength, modules of bending and electrical conductivity. Thus, such organic polymers with high modulus of elasticity in bending as polyamides, polyimides, and aramids, metals, glass and other ceramics, carbon fibers and graphite fibers, are suitable for use with materials. Examples of glass fibers include E-glass and S-glass. E-glass is low aluminum-borosilicate composition with excellent electrical properties and good strength and modulus of elasticity. S-glass is a magnesium-aluminosilicate composition with significantly improved strength modules of elasticity. Rovings in the parallel beam with a small twist or without it. Fiber-reinforced composites can be used in aviation, aerospace engineering, marine, vehicles, and other applied fields of application. They can also be used as structural materials and corrosion-resistant agents. In addition, they can also be used for the production of containers, electrical parts and electronic devices and other consumer products.

The following examples are given to illustrate the invention and in no way limit the scope of its claims. Unless otherwise noted, all parts and percentage compositions are weight.

Examples

In the examples used the following materials:

DowanolD: Simple methyl ester dipropyleneglycol, the solubility parameter of 9.3, a product of The Dow Chemical Company.

D. E. R.383: Liquid epoxy resin based on bisphenol a, having an epoxy equivalent weight (EPW) 180, a product of The Dow Chemical Company.

Catalyst a-2: Acetate tetrabutylphosphonium (70% solution in methanol).

GMAA: Glacial methacrylic acid.

DMP 30: Tris-2,4,6-dimethylaminomethylphenol.

Mecr: methyl ethyl ketone Peroxide.

Clay: 27% wt. dispersion hectorite in propylene glycol.

Clay: Na-montmorillonite, the silt.

DMA: N,N-dimethylaniline.

For the characterization of polymer composites were used the following methods.

The x-ray diffraction (XRD)

XRD measurements made on the record of the nanocomposites nanocomposite using SR x-ray source. X-rays measured between 1.5 and 452q. The intensity of x-ray radiation corresponded to the intensity of the dispersion polymer.

The position of peaks were measured graphically and approximatively to the maximum peak. The estimated error of measurement of the position of the peak was approximately 0,2q. The measurement error may be larger, depending on the peak intensity, peak width and any displacement of the sample in the x-ray equipment from the ideal height of the sample.

The position of the peak was used to calculate the d-space peak, on the basis of the law Bragg's:

nI=2d(Sin q),

where I is the wavelength of x-rays in; d-d - space; and q is equal to half of the diffraction angle,2q; n is an integer and has a value of "I".

Presents both the - d parameter - space and/or the position of the peak.

Transmission electron microscopy

Epoxy samples cut in quaceance slices with the thickness of about 80 nanometers. The slices were placed on a grid of THE electron microscope for testing in a transmission electron microscope (THEMES).

Example 1

A. Obtaining clay And

The hydrate of magnesium chloride (13 g) dissolved in water (600 ml) and stirred. After the solution has become transparent, add the 2N ammonium hydroxide solution (88 ml). Add water to a total volume of 800 ml and stirred for one hour. Then the precipitate allowed to settle. Water decantation from the sediment. Solid magnesium hydroxide is washed with 500 ml of water and decanted. Repeat the washing 2N silver nitrate until then, until you have determined the chloride ions in desantirovanii fluid. The washed magnesium hydroxide is dried at 60C for 16 hours. Magnesium hydroxide (14,96 g) dissolved in water (800 ml). In a separate container and add water (928 ml) lithium fluoride (1,76 g). Both solution stirred until then, until they become homogeneous (about 10 minutes). Then, two solutions are poured together in a 4-liter beaker. The combined solution is stirred for 20 minutes. Then in 4-liter laboratory glass add propylene glycol (938 g) and water (368 ml). To the drug immediately after the addition of the glycol type colloidal silicon dioxide (73,6 g). Water is added to �https://img.russianpatents.com/chr/176.gif">With over 12 days. After completion of the synthesis the preparation is centrifuged at 1500 rpm for 30 minutes. Centrifuged product is decanted, the product, add 2 liters of water and stirred. Wash water again centrifuged at 1500 rpm for 30 minutes. Two-liter washing was repeated twice, decanter water after each flush. After the last wash, the product is placed in a drying cell from PYREX55With the oven for more than 7 days. To confirm the number of hectorite in the final product, as well as to confirm that the water is completely removed from the final product, made by TGA (thermogravimetric analysis). TGA showed that 26.68% of the product is Li-hectorite.

C. Obtaining a composite material: unsaturated-simple polyester/clay

Isophthalic acid (269/42 g) is mixed with the clay dispersion As obtained in part A. to remove water from the mixture of the reaction product, the mixture is heated to approximately 200C. the Reaction mixture is cooled to approximately 160C. In the reaction vessel add an additional amount of propylene glycol (372,2 g) and maleic anhydride (635,54 g). R styrene monomer (890,9 g) to the polymer type hydroquinone, inhibitor (0.29 grams). Radiograph of the product is shown in Fig.1.

Example 2

Unsaturated polyester, such as an ester of DCPD (Dicyclopentadiene), synthesized using 50% EC(ethylene glycol) and 50% of DEG (diethylene glycol), diluted with styrene, mixed with clay C. Clay is dispersed mechanically and with the help of ultrasound. The final loading of the clay is a value between 2 and 6 weight percent. For the subsequent curing of the composition of the use of 0.2 weight percent of naphthenate With and 1.25 weight percent of MCR. The resulting composite shows an increase of the base space of the clay from about 19 to more than 38observed on the radiograph shown in Fig.2.

Example 3

Clay is dispersed in D. E. R.383 during the initial download of about 6 weight percent. D. E. R.383/clay In use in the synthesis of composite complex vinyl ester/clay.

Resin-based epoxiconazole of ester receive, by placing the reactor under a stream of nitrogen D. E. R.383/clay (4502 g), bisphenol a (167,6 g) and catalyst a-2 (0,383 g) and allowing the resin to achieve the desired epoxy equivalent (EEW). The resin is heated to 65.582.gif">383/clay (168,5 g) to reduce EEW to a predetermined value EEW.

The temperature of the reactor is reduced to a temperature below 90C.

As soon as the temperature drops below 90With, instead of the current nitrogen bubbled air flow. Add hydroquinone (0,690 g) and GMAA (169,1 g).

When the temperature reaches 80To add DMP-30 (1.18 g). The temperature is slowly increased to 118C. the Reaction is carried out up until the acid content is not reached 1.1 percent. Titration of acid and epoxide spend every hour after the temperature reached 118C. the Percentage of acid should be from 0.2 to 0.4 percent. When the acid reached 1/1 percent, the heating stops and add inhibitor (oxalic acid) with styrene (400 g). As soon as the temperature has dropped below 100C, add the additional amount of styrene (383 g). The resin is left to cool and Packed.

A sample of the resin based on vinyl ester taken from the packaging before adding styrene. The radiograph of the sample shown in Fig.3.

After complete addition of the styrene portion of the resin utverjdayut. X-ray is s specialists in a given field of technology it is shown in Fig.4. THE image of the structure shown in Fig.5.

The second portion of the resin utverjdayut VRO and DMA using methods known to experts in this field of technology. Radiograph of the cured composition shown in Fig.6. THE image of the structure shown in Fig.7.

Caulk samples were obtained by mixing 18 g of clay 282, resin. The mixture of resin and clay then catalyze the corresponding catalysts. The polymer composition is then poured into the mold. The mold is placed in an oven at 110With over 2 hours. The mold is cooled down to room temperature before removing from it the cured sample of the resin. Radiograph of a composite material based on vinyl ether complex is shown in Fig.8.

The peaks of x-ray radiation for x-ray shown in Fig.1, 2, 3, 4, 6 and 8, described in the table.

Claims

1. Polymer composite comprising a matrix representing epoxygenase ester resin and dispersed therein capable of swelling the layered inorganic material having organophilicity properties due to embedded organic material after the contains from 20 to 60 wt.% Monomeric styrene.

3. Polymer composite under item 1, characterized in that the resin-based epoxiconazole of ester bromirovanii and contains 40 wt.% Monomeric styrene.

4. Polymer composite under item 1, characterized in that the resin-based epoxiconazole of ester is the liquefied resin-based epoxiconazole of ester containing 40 wt.% Monomeric styrene.

5. Polymer composite under item 1, characterized in that it is capable of swelling the layered inorganic material is layered or layered silicate aluminate, or a mixture.

6. Polymer composite under item 5, characterized in that the layered silicate is montmorillonite, hectorite, saponite, nontronite, beidellite, volkonskoit, sauquoit, magadia, memetic, ceniai or vermiculite.

7. Polymer composite under item 6, wherein the layered silicate has a cation exchange capacity of between 20 and 200 milliequivalents 100 grams of layered material .

8. Polymer composite under item 6, characterized in that the layered silicate contains viewy ion.

9. Polymer composite under item 8, characterized in that oniony ion contains at least one fragment, which gives the silicate organophilicity.

10. Polymer composite under item 8, otlichalis is audica fact, the ammonium cation is a primary, secondary, tertiary or Quaternary ammonium cation.

12. Polymer composite under item 6, characterized in that the layered silicate is at least 0.01 wt.% and not more than 90 wt.% the final composite.

13. Polymer composite under item 6, characterized in that the layered silicate or layered illuminate in polymer composite has a large interlayer space than silicate or aluminate prior to its introduction into the polymer matrix.

14. Polymer composite under item 1, characterized in that it is made in the form of coatings, films, foams, laminates, fibers, hot-melt adhesive or molded products .

15. Polymer composite comprising a matrix representing epoxygenase ester resin or unsaturated complex polyester, or mixtures thereof and dispersed in the resin, capable of swelling the layered inorganic material having organophilicity properties due to embedded organic material layer is 27% dispersion of clay hectorite in propylene glycol.

16. Polymer composite under item 15, wherein the unsaturated complex polyester obtained by condensation of (a) Ethylenediamine dicarboxylic or polycarboxylic acids or anhydrides of di - or polycarboxylic acid is phthalic acid, ISO - or terephthalic acid, adipic acid, succinic acid, sabotinova acid, maleic acid, fumaric acid, Tarakanova acid, harpalinae acid, allinternal acid, taconova acid, musicanova acid, citric acid, pyromellitate acid, tremezzina acid, tetrahydrophtalic acid or thiodiglycolic acid.

18. Polymer composites for PP.15 and 16, characterized in that diola or polyol is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropyleneglycol, glycerol, 2-Butin-1,4-diol, gidrirovanny bisphenol a, simple listenerdatatype ether, simple biphenyldicarboxylic ether or neopentylglycol.

19. A method of obtaining a polymer composite, which consists in mixing the components of the polymer composite according to PP.1-14 or 15-18.

20. The method according to p. 19, characterized in that the inorganic layered material polymer composite on PP.1-14 added anionic or neionogennye inorganic material layer.

21. A fibre-reinforced composite, comprising a cured binder based polymer composites for PP.1 - 14 or 15-18, reinforced by one or more reinforcing fiber or frame.

 

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