BRPI0901987A2 - composite, process for the production of a composite and a modified mineral, product and use thereof - Google Patents

Abstract

COMPOSITE, PROCESS FOR THE PRODUCTION OF A COMPOSITE AND A MODIFIED MINERAL, PRODUCT AND USE OF THE SAME. The present invention relates to composite materials having good mechanical properties (and high optical clarity or transparency), and the process of their production. The composite material comprises at least one polymer and a mineral dispersed therein. In particular, the present invention relates to composites comprising: a) a mineral containing amphoteric or acidic groups; and b) at least one hydrophobic polymer; wherein the mineral is reacted with at least one compound of the formula RnXHm, in which: XéO, NouS; the sum of the group number of the element X in the Periodic Table of the Elements, of n and m is equal to 8; and R is an alkyl radical of 3 to 50 carbon atoms, linear or branched, substituted or unsubstituted, aliphatic, cyclic or aromatic, and where the weight ratio of the mineral to the hydrophobic polymer is from 10:90 to 0 , 1: 99,9, preferably from 7:93 to 1:99, more preferably from 2.5: 97.5 to 1:99. In addition, the present invention relates to the process of preparing the composite described above, the product containing it and its uses. The present invention also relates to the production process of a modified mineral.

Description

Patent Descriptive Report for "COMPOSITE, PROCESS FOR PRODUCTION OF A COMPOSITE AND MODIFIED MINE-RAL, PRODUCT AND USE OF THE SAME".

Field of the invention

The present invention relates to composite materials having good mechanical properties (and high optical clarity or transparency), and the production process thereof. The composite material comprises at least one polymer and a modified mineral dispersed therein.

Summary of the Invention

Polymer and mineral composites have desirable properties for many commercial applications. These composites are stiffer and stronger and have improved barrier properties when compared to glass or mineral reinforced polymers with lower inorganic material content and are therefore lighter in weight. In addition, these polymer and mineral composites have improved thermal stability and fire self-extinguishing properties. Composites with these characteristics have a wide range of applications: examples for such applications are paints, varnishes, enamels, liquid resins, epoxides and others.

Brief Description of the Prior Art

Polymer and mineral composites achieve composite properties at much smaller reinforcement volume fractions, thus avoiding many of the expensive and difficult fabrication techniques that are common for conventionally fiber or mineral reinforced polymers. Known methods of preparing polymer and mineral composites involve forming the polymer in situ or performing intercalation by melting the pretreated polymer.

U.S. Patent No. 4,455,382 teaches the production of a polar liquid to disintegrate a glass / ceramic body prior to reaction with organic polyols to form the interlayer of crystals to form an organic-inorganic composite.

U.S. Patent No. 4,739,007 teaches the use of an aqueous swelling agent mixed with a ground clay material, followed by ion exchange with an organic cation previously mixed with the swelling stock to produce a composite material.

U.S. Patent No. 4,894,411 expands this method by introducing a polyamide monomer as the organic cation followed by polymerization of the monomer by heating in the presence of a phenol or polyamine stabilizer.

US Patent No. 4,810,734 teaches the mixing of a layered clay with a swelling agent to form a complex, which is mixed with a monomer to intercalate into the layered material, followed by polymerization of the monomer to form a complex material. purpose.

U.S. Patent No. 5,955,535 teaches the intercalation of a polymer in the galleries of an Iamelar silicate by heating the polymer-silicate mixture above the melt temperature or glass transition temperature of the polymer in the absence of a solvent. This method produces polymer-clay composites with small visible grains of organically modified clay and other suspended impurity materials, thus limiting potential use in applications requiring transparency and temperature resistance.

GB 1,203,360 provides a process for generating water repellent properties for inorganic compounds comprising treating said inorganic compound in a finely divided form of a long chain alcohol at elevated temperatures. However, this document only refers to silicates and not to clays.

GB 1,370,253 relates to a composition comprising a mixture of a cation-modified organophilic clay and a volatile organic vehicle, as well as a welding method. In this document, it is described how cation-modified organophilic clay can be prepared by converting the organic bases to the salts by the addition of an acid.

In view of the above, a new method for producing polymer and clay composites resulting in a transparent composite with better thermal properties is provided. Brief Description of the Invention

The present invention relates to composites comprising:

a) a mineral containing amphoteric or acidic groups; and

b) at least one hydrophobic polymer;

wherein the mineral is reacted with at least one compound of formula RnXHm, in which:

X is O, N or S;

the sum of the group number of element X in the Periodic Table Elements, of η and m is equal to 8; and

R is an alkyl radical of 3 to 50 carbon atoms, linear or branched, substituted or unsubstituted, aliphatic, cyclic or aromatic, and

wherein the weight ratio of the mineral to the hydrophobic polymer is from 10:90 to 0.1: 99.9, preferably from 7:93 to 1:99, more preferably from 2.5: 97, 5 to 1:99.

The present invention may also be carried out with greater weight ratios of mineral to hydrophobic polymer. For example, weight ratio may be 30:70 or 40:60. However, better results are obtained when the weight ratio is from 10:90 to 0.1: 99.9.

The mineral of the present invention may be selected from the group consisting of silicates, carbonates and metal oxides with amphoteric or acidic groups. Preferably the silicates are crystalline silicates containing galleries (clays).

Preferably, the mineral used in the composite may be selected from the group consisting of smectite, mont-morilonite, kaolinite, hectorite, fluorhectorite, hydroxyl hectorite, saponite, laponite, and combinations thereof, preferably smectites and cau-linites.

Preferably, the mineral of the present invention is a smectite or kaolinite containing a cation selected from the group consisting of sodium, potassium, lithium, and calcium, such as sodium montmorillonite or sodium kaolinite.

In a preferred embodiment, R is selected from the group consisting of hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, 2-methylhexyl, 3-methylhexyl, 2 -methylheptyl, 3-methylheptyl, 2-methyloctyl, 3-methyloctyl, 4-methyloctyl, 2-ethylhexyl, 2-ethylheptyl, 3-ethyloctyl, benzyl, methylbenzyl, ethylbenzyl, toluyl, xylene nonyl phenyl, cyclohexyl, cycloheptyl and cyclooctyl.

Suitable examples for the compounds of the formula RnXHm are hexanol, heptanol, octanol, dodecanol, hexadecanol, octadacanol, 2-aminomethylpropanol, hexylamine, dihexylamine, heptylamine, diheptylamine, octylamine, dioctylamine, nonylamine, dinonylamine, dodecylamine, didodecylamine hexadecylamine, dihexadecylamine, octadecylamine, dioctadecylamine, di (2-ethylhexyl) amine, di (2-methoxyethyl) amine, 3- (2-aminoethylamino) propylamine, diisopropylamine, oleylamine, tallow, dicocoalkylamine and cocoalkylamine.

Preferred compounds of the formula are those which have their boiling point above 100 ° C, preferably above 150 ° C.

The polymer used in the composite may be a thermoplastic or thermosetting polymer, preferably a thermoplastic polymer. As an example, the polymer may be selected from the group consisting of vinyl polymers, polyalkylene oxides, polyesters, devinylidene polymers, fluorine polymers, polysiloxanes, polyphenylene sulfide, polyketals, polycarbonates, polysulfones, polyether sulfones, resins phenolic, epoxy resins, alkyd resins, furan resins, urea resins, melamine resins, polyurethanes resins and aniline resins.

The polymer may be a recycled material or a mixture of virgin and recycled polymers, wherein the amount of virgin polymer in weight is 1 to 50% of the total polymer fraction in the composite, preferably less than 10% by weight. Preferably, the recycled and virgin polymers are from the same family of polymers.

The polymer used in the composite should preferably be a vinyl polymer, a polymer based on ethylene monomers, propylene monomers, styrene butadiene based monomers butadiene base and styrene vinyl chloride based monomers. , and based on amides. Preferably, polyethylene (PE), polypropylene, polystyrene and / or polycrylates should be used.

In preferred embodiments, the composite of the invention comprises:

(a) at least one ethylene monomer-based polymer and at least one smectite or silicate-based mineral;

b) at least one polymer based on ethylene monomers and at least one kaolinite or carbonate based mineral;

c) at least one propylene monomer-based polymer of at least one smectite or silicate-based mineral;

d) at least one propylene monomer-based polymer of at least one kaolinite or carbonate-based mineral;

e) at least one styrene monomer-based polymer and at least one smectite or silicate-based mineral;

f) at least one propylene monomer-based polymer and at least one kaolinite or carbonate-based mineral.

Another preferred embodiment of the present invention is the use of at least two different polymers to be mixed together to form a mixture that can be used in polymerization of monomer units. Examples for such polymers are SBR (styrene-butadiene copolymer rubber), PA (polyamide), PP (polypropylene), PVC poly (vinyl chloride), PE (polyethylene) and immiscible polymers.

The present invention also relates to a cable or wire containing the composite described above.

The present invention also relates to the process for producing the modified mineral comprising the following steps:

(a) provide a mineral containing amphoteric or acidic groups,

b) reacting the mineral of step a) with at least one compound of formula RnXHm, wherein: X is Ο, N or S;

the sum of the group number of element X in the Periodic Table Elements, of η and m is equal to 8; and

R is an alkyl radical of 3 to 50 carbon atoms, linear or branched, substituted or unsubstituted, aliphatic, cyclic or aromatic,

wherein step b) is performed at a temperature range of 30 ° C to 300 ° C and with vigorous stirring; thus forming a low molecular weight component and the modified mineral; and

c) eliminating the low molecular weight component formed in step b).

Preferably the temperature of step b) is at least 10 ° C, preferably at least 50 ° C, higher than the boiling temperature of the low molecular weight component. For example, if the under molecular weight component is water, the temperature of step b) should be above 110 ° C, preferably above 150 ° C.

In a preferred embodiment of the present invention, the mineral passes through mesh screen 200, preferably mesh screen 325 and more preferably mesh screen 500 before reacting a compound of formula RnXHm. In particular, the mineral has an iron and / or titanium content (calculated as oxides) of less than 3%.

The present invention also relates to the modified mineral obtained by the process described above.

The composite of the present invention may be produced by the process comprising the following steps:

The. provide a mineral containing amphoteric or acidic groups,

B. reacting the mineral from step a) with at least one compound of formula RnXHm, in which:

X is O, N or S;

the sum of the group number of element X in the Periodic Table Elements, of η and m is equal to 8; and

R is an aliphatic, cyclic or aromatic linear or branched, substituted or unsubstituted alkyl radical of 3 to 50 carbon atoms, wherein step b) is carried out in the temperature range from 30 ° C to 300 ° C and with stirring vigorous; thus forming a low molecular weight component and the modified mineral; and

c) eliminating the low molecular weight component formed in step b); and

d) modifying the above described mineral formed in step b) to make at least one hydrophobic polymer, thereby forming the composite.

Particularly, step d) is performed with a very vigorous mixing and under conditions of temperature, pressure and / or crosslinking that allow a good workability of the chosen polymer. Preferably, step d) is carried out at temperatures above the polymer melt temperature for polymer systems that may be extruded or injected.

The composite obtained by this process may be subjected to other steps or processes such as melt extrusion, injection or other processes that allow the composite to be transformed into other forms.

Preferably the temperature of step b) is at least 10 ° C, preferably at least 50 ° C, higher than the boiling temperature of the low molecular weight component. For example, if the component under molecular weight is water, the temperature should be above 110 ° C, preferably above 150 ° C.

In a preferred embodiment of the present invention, the mineral passes through mesh screen 200, preferably mesh screen 325 and more preferably mesh screen 500 before reacting with the compound of formula RnXHm. Preferably the mineral has an iron and / or titanium content (calculated as oxides) of less than 3%.

Preferably, the process of the present invention comprises the step of mixing the clay or mineral and polymer in a mixer, followed by a 5 minute to 24 hour rest.

The process of the present invention may further comprise integrating the mineral into the polymer by an extrusion process.

The composite of the present invention may be transparent. Due to their improved performance, composites can be used in packaging and engineering applications, in the automotive industry, in mold making, in construction, in paints, in electronics, in textiles, as a plasticizer, as a modifier. of rheology, for the absorption of oils, as an agent that improves the miscibility of immiscible or barely compatible systems, as an agent that improves fatigue resistance, as an agent that improves the flow behavior of the polymer.

Detailed Description of the Invention

The method of the present invention relates to the formation of a polymer modified mineral to form a mineral containing amphoteric or acidic groups and a polymer containing polar or polarizable moieties. Preferably, the polymer contains low amounts of polarized or polarizable portions, although the method of the present invention also works when the polymer contains larger amounts of polarized or polarizable portions.

In a preferred embodiment of the present invention, the mineral starting material is a gallery containing crystalline silicate. One possibility of the crystalline starting material is the crystal of the Iamelar silicate which consists of two layers of tetrahedral silica fused to a shared margin octa-hydrochloric sheet consisting of aluminum and magnesium hydroxides. These Iamellar silicates or tipomica Iamellar silicates are also called MTS. The arrangement of the Iamelas provides interlayers or galleries between the coverslips.

Galleries are usually occupied by cations that balance the deficiency of charges that is generated by isomorphic replacement within the layers. In addition to these charge balance cations, water is also present in the layers where it attempts to associate with cations. Silicates are termed to contain galleries to denote the layers between the crystal leaves where the associated cations and water are found.

Such silicates include smectite clay minerals (e.g., montmorillonite, saponite, beidelite, nontronite, hectorite and stevensite), vermiculite, haloisite, kaolinite, or synthetic silicates such as exemplolaponite, fluorhectorite, and hydroxyl hectorite. In addition, semisynthetic silicates which are composed of solid solutions of any of the structurally compatible synthetic silicates and natural silicates such as talc, fluortalco, polylithiteite, and fluorpolylithiteite may be produced.

Another possibility for crystalline starting material may be crystal of Iamelar silicate of the type found in kaolin.

Preferred silicates are smectite and cau-linite clay miners and the most preferred silicate is montmorillonite and kaolinite and the most preferred silicate is kaolinite.

The gallery-containing silicates of the present invention are normally associated with charge balance cations selected from the group consisting of sodium, potassium, lithium, calcium and magnesium ions.

In the prior art, intercalation of polymers, which do not contain hydrophilic groups, in galleries cannot be performed when these charge balance cations are present in the conventional form (i.e. as sodium, potassium, lithium, calcium and ions). magnesium).

Therefore, charge balance cations should be replaced by organic cations containing at least one organophilic group for subsequent mixing with the hydrophobic polymer. As a result, silicates need to be modified to contain these organic cations through ion exchange processes as taught by Okada et al (US Patent No. 4,739,007 and 4,894,411) and Kawasumi et al (US Patent No.04,810,734). ). This disadvantage is solved by the present invention.

Organic cations capable of replacing naturally occurring charge balance cations of the prior art include, for example, substituted ammonium ions (such as octadecyl dimethyl ammonium ions or dodecylammonium ions) or other mono or di-C 18 -C 18 alkylammonium ions or R-COOH where R represents an alkylene group which may contain phenylene, vinylene, branches and / or other groups (such as 12-amino-dodecanoic acid ions) or organophosphonium ions (such as C8 -C8 alkylphosphonium ions) or organosulfonium ions (such as C8 -C18 alkylsulfonium ions). For the prior art, the preferred organic cations are ammonium ions and most preferred is the n-octadecylammonium organic cation. These cations, mentioned as a problem in the state of the art, are no longer needed in the mineral of the present invention. (In the present invention intercalation is possible even in the presence of sodium, potassium or other ion.)

In a preferred embodiment of the present invention, the mineral is, prior to use, purified to reduce impurities.

In the first stage of the state of the art, charge balance cations naturally present within the silicate galleries are replaced by an organic cation. The cation exchange process can be carried out by two routes.

In the first route, the cation exchange process can be done in pure water. Natural or activated clay is usually dissolved in low concentrations in water and then treated with organic cation. Cujocátion clay has been changed and is usually insoluble in water. Through drying filtration, onium clays of the state of the art can be obtained.

"Onium clay" is a generic description of state-of-the-art clays prepared via organic cation exchange reactions in clay. Typically, organic cations are based on ammonia and phosphonia. Since their English suffix is "onium" and as they react with clay under decation, the product is an "onium clay".

In the second route, the ion exchange reaction is performed in solution of, for example, equal parts of ethanol and water. The gallium-containing silicate swells and is suspended in the aqueous solution (ethanol) to produce a cloudy suspension of silicates with the organic cations associated with negatively charged regions on the surface of the crystal structure.

Thus, the organic cation-coated silicate particles form micelles in the aqueous ethanolic solution. Such a suspension is then filtered by means known in the art to remove remaining undissolved crystalline solids of a particle size greater than 10 µm. The resulting filtered suspension containing the organic cation introduced into the silicate micelles is mixed with a solvent and allowed to stand preferably between 12 hours and 48 hours, more preferably 24 hours to 36 hours. During this time, the water in the aqueous ethanolic solution separates from the organic solvent producing a double layer of organic solvent and water.

The aqueous layer is decanted, thus retaining the organic solvent layer containing the organic cation introduced into the dosilicate micelles. The organic solvent serves as a medium in which the micelles are uniformly mixed with the polymer to form the clay and polymer composite product.

Suitable solvents include organic solvents such as chloroform, other chlorinated hydrocarbons such as ethyl chloride, fluorinated hydrocarbons such as fluorbenzene or 1-fluorpentane, brominated hydrocarbons such as bromoform or bromobenzene, hydrocarbons such as 1-iodopentane or iodobenzene, such as hydrocarbons. cyclohexane, heptane, aromatic hydrocarbons such as toluene or benzene, ethers such as diethyl ether, petroleum extracts such as petroleum, or gasoline. Often the preferred solvent is chloroform. The solvent may be removed by any means known in the art to recover the powdered micelles. For example, the solvent may be removed under vacuum, oven drying or evaporation. Preferably, the solvent is evaporated if recovery of the powdered micelles is desired.

The use of solvent is a disadvantage, which increases the time, cost and environmental impact of the process. In the present invention, solvent use is no longer necessary since silicate is no longer treated to replace natural ions with organic ions. Thus, the method of the present invention is efficient in time, cost and environmental impact as it does not contain the step in which solvents are used.

The polymer to be mixed with the mineral may be thermoplastic or thermoset, although thermoplastic polymers are preferred.

Examples of thermoplastic polymers include vinyl polymers (e.g. polystyrene, polyethylene, polypropylene, poly (vinyl chloride), polymers based on ethylene propylene diene monomers, deacronitrile styrene-butadiene and rubber copolymers), polyalkylene oxides (e.g. e.g. poly (ethylene oxide)), polyamides (e.g. nylons, such as nylon-6 (polycaprolactam), nylon-66 (poly (hexamethylene adipated)), nylon-11, nylon-12 , nylon-46, nylon-7, or nylon-8), polyesters (for example, poly (ethylene terephthalate) and poly (butylene terephthalate)), devinyl polymers (e.g. poly (vinylidene fluoride) and poly ( vinylidene chloride)), fluorinated polymers (eg poly tetrafluoroethylene and poly chlorotrifluoroe-tylene), polysiloxanes (e.g. poly dimethylsiloxanes), polyphenylene sulfide, polyacetals, polycarbonates, polysulfones and polyether sulfones which may be present alone or with a mixture, a copolymer, the a block polymer.

Preferred examples of thermoplastic polymers are vinyl group polymers (especially polystyrene, polyethylene, polypropylene, poly (vinyl chloride), polymers based on ethylene propylene die-monomers, acrylonitrile styrene-butadiene and rubber copolymers), vinyl polymers ( poly (vinylidene fluoride) and poly (vinylidene chloride)), fluorinated polymers (e.g. polytetrafluoroethylene and polychlorotri fluoroethylene).

Preferred polymers are vinyl polymers wherein polystyrene, polyethylene, polypropylene and polyvinyl chloride are especially preferred.

Examples for thermosetting polymers are phenolic resins, epoxide resins, unsaturated polyester resins, alkyl resins, furan group resins, urea group resins, melamine resins, polyurethane resins and anilin resins which may be present. alone or with a mixture, a copolymer, or a block polymer.

Additionally, the polymer may be of virgin or recycled material.

Virgin material means a material obtained by a transformation process, where the starting materials used are used for the first time in the transformation process. For example, polypropylene or polyethylene pellets made of the polymerized material may be extruded or other processes may be used to give a different shape to the polymer. In this example, as the polymer first undergoes the process, the product or material obtained is called a virgin.

After the use of a virgin material it can be transformed into other shapes and applications by a very wide range of techniques. This would be the second time this material has undergone a transformation process anyway. The resulting material is called recycled material. This denomination has nothing to do with the use of these materials. It does not indicate the value, use or destination of the material. Thus, if a material has once undergone the transformation process, that material is called a virgin, and if the material has undergone more processes of transformation, it is called recycled material.

In a preferred embodiment of the present invention, the polymer is in its recycled form.

Recycled material is a mechanically stressed material such that its own workability, without any additives, is no longer appropriate. Thus, the use of recycled polymer is not possible in the production or processing line. For example, the mass coming out of the extruder is so inconsistent that pellets cannot be formed since the mass disintegrates before it passes the cooling bath. In practice, the skilled artisan attempts to improve the workability of recycled material by adding virgin polymer material. This addition may improve workability, but the stiffness and elongation of these materials are not satisfactory. This is why a system that guarantees improvements in mechanical properties is desired.

In a preferred embodiment of the present invention, a clay consisting of a modified mineral in admixture with mixed depolymer systems consisting of virgin and recycled material is used. The virgin material content in that mixture may be up to 50% by weight.

An especially preferred embodiment of the present invention is the use of clay consisting of minerals in admixture with a polymer system consisting only of recycled material and no virgin material.

Another preferred embodiment of the present invention is the use of two polymers, which are normally immiscible. For example, the mixture PE (polyethylene) and PA (polyamide) is usually not stable. Using the compounds of the present invention, such immiscible polymers can be made miscible and the composite formed exhibits extra performance.

The chosen polymer and mineral are mixed at room temperature under vigorous stirring in a mixer. A non-limiting example for blending is the typical binder used to process polyethylene or polypropylene, especially in the case of recycled polymeric material. Other blending techniques, such as the ribbon-blend mixer, knea-der or others known to one skilled in the art, may also be used. This method allows a premix and, through rigorous mixing, a better orderly arrangement of the mineral in the polymer phase is achieved. An example, but not a limiter, for the rigorous mixing is the typical extrusion of the melt above the melt temperature of the chosen polymer.

The interactions between polymer and mineral are completed within a few minutes at extruder temperature. The choice of polymer to use largely defines the parameters in the blending phase. Thus, the temperature range to be used in the blending phase is where the polymer chosen has the best workability. Boat performance can only be guaranteed by choosing the appropriate equipment. The extruder must meet all requirements of the chosen polymer. Temperature and time parameters are defined by the technical parameter fusion flow index (MFI). This index defines the flow behavior of the chosen polymer at certain temperatures. The parameters chosen should be such that the polymer in question has a good flow, which may be influenced by the time of warming up and temperature.

Using dynamic conditions (mixing and shaking) during this process can improve the temperature and / or time required to complete the interaction. The mineral adopts a conformation in which the mineral layers are more separated than in a purely physical mixture without aglutination and / or extrusion.

Polymer-mineral composites have improved tensile strength, greater modulus of elasticity (at least an increase of more than 10% and greater than with untreated minerals) and elongation to greater rupture of about 1% to 200%, depending the amount and type of mineral incorporated in the polymer and the specific properties of the mineral used. This behavior is qualitatively different from that presented by the mass polymer and can be attributed to the interaction of the polymer chains in the micellar structure of the mineral. Polymer-mineral composites have better dimensional stability and improved tensile strength compared to unmixed polymers.

The mineral can be pure or mixtures of various minerals. For example, for the clay group, the minerals may be selected from the group consisting of smectite, montmorillonite, ca-linite, hectorite, fluorhectorite, hydroxyl hectorite, saponite, laponite, and combinations thereof. Also kaolinite clays can be used.

Preferred clays are smectite and kaolinite type, more preferred are kaolinite type. Non-limiting examples of clay materials: vermiculite, muscovite, kaolinite, pyrophyllite, talc, hectorite, haloisite, smectite, montmorillonite, boehmite and illite. The silicate material may also contain other silicon based materials or other minerals. Examples for these materials are quartz, feldspar, rutile, anatasa, epsomite (hydrated magnesium sulfate), hematite, analyte (hydrous sodium aluminum silicate), barium silicate, calcite, iron sulfate (hydrated), carbonate sodium (hydrated), dolomite, bauxite. The most preferred clays are smectites and kaolinites.

In addition, the most preferred mixtures are equartzo kaolinites, muscovite and quartz. The extruded and molded body according to the present invention may optionally comprise additives, for example other types of fillers, and reinforcing material such as fibers. glass or talc, flame retardants, foaming agents, stabilizers, anti-blocking agents, gliding agents, acid scavengers, antistatic agents, flow promoting agents and dyes and pigments.

The highly rigid polyolefin-based composite materials of the present invention are suitable for the production of molds, for example by injection molding or extrusion compression.

Polyolefin-based composite materials can be used in mold making, but can also be mixed, for example, with unmodified polyolefin, polyolefin-based composite materials, which contain high percentages of mineral, can be viewed as main batches and may be mixed with unmodified polyolefins to achieve a lower mineral content in the mold as a whole. Polyolefin-based composite materials according to the present invention are also suitable for producing components for the automotive industry.

For many of these components good rigidity is required even at elevated temperatures. Examples for such components in the car are dashboards, bumpers, fenders and hoods.

In general, these composites can be used in all fields of application where polymers can be employed, and requirements for conventional polymer mechanical behavior can be a problem. An example to clarify such a problem is plastic bags, especially when the polymer is a recycled material, which cannot handle high weights. Polyolefin-based composite materials according to the present invention have a larger modulus of elasticity and thus are more suitable for such load-demanding applications.

In polyolefin-based materials according to the present invention, an additional polar polymer may be present, such as nylon, styrene / acrylonitrile (SAN) copolymer, acrylonitrile / butadiene / styrene (ABS) terpolymer. carboxylic acid / styrene anhydride copolymer or carboxylic acid / styrene copolymer (such as for example styrene / maleic acid anhydride (SMA) copolymer). Preferably nylon (or polyamide) is present.

The resulting polymeric composition is, by virtue of its components, a well-matched blend of a polyolefin with a nylon. 4,6), as well as other known nylon, can be used.

The mineral undergoes a transformation process comprising the following steps:

(a) provide a mineral containing amphoteric or acidic groups,

b) reacting the mineral of step a) with at least one compound of formula RnXHm, in which:

X is O, N or S;

the sum of the group number of element X in the Periodic Table Elements, of η and m is equal to 8; and

R is an alkyl radical of 3 to 50 carbon atoms, linear or branched, substituted or unsubstituted, aliphatic, cyclic or aromatic,

wherein step b) is performed at a temperature range of 30 ° C to 300 ° C and with vigorous stirring; thus forming a low molecular weight component and the modified mineral; and

c) eliminating the low molecular weight component formed in step b).

This process can be performed in conventional reactor systems, such as kneaders, where a good domineral mixture can be successfully achieved at set temperatures.

Also other sources that introduce energy into the lightning system can be used. Examples for these sources are microwaves, ultrasound, light of any length and intensity that does not degrade the reagents. Other sources, even if not specifically mentioned, may also be used.

The transformation process can also be carried out with the help of a co-agent. For example the mineral may be mixed with the solvent, for example hexadecanol and hexanol may be used as co-solvents. This liquid medium may be advantageous for some processes but does not directly interfere with the mineral during the reaction. As this option makes cleaning steps necessary, the preferred way to produce the minerals according to the present invention is to mix a system without use of solvent or liquid.

The system should allow good interaction with the reagents. There are many equipment and appliances that fulfill this need. For example, bakery dough mixing machines with a heating apparatus, mills with a heating apparatus and others may be used depending on physical properties of mineral or other ingredients. A good mix under heating is important.

A preferred embodiment is a solvent free process.

The mineral may, in a solvent free process, react with at least one compound of the formula RnXHm, wherein X is O, N or S and the sum of the group number of element X in the Periodic Table of Elements of η and of m is equal to 8.

The mineral may, in a solvent free process, also react with at least one compound of the formula RY, where Y is chlorine, iodine, fluorine.

In the compounds of the formulas RnXHm and RY, R is an alkyl radical of 3 to 50 carbon atoms, linear or branched, substituted or unsubstituted, aliphatic, cyclic or aromatic

Preferably R is selected from the group consisting ofhexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, 2-methylhexyl, 3-methylhexyl, 2-methyl -heptyl, 3-methylheptyl, 2-methyloctyl, 3-methyloctyl, 4-methyloctyl, 2-ethylhexyl, 2-ethylheptyl, 3-ethyloctyl, benzyl, methylbenzyl, ethylbenzyl, toluyl, xylene, no-nylphenyl cyclohexyl, cycloheptyl and cyclooctyl.

Examples of the compounds of formula RnXHm are HNR2 (where N = 5, m = 1 and η = 2), H2NR (where N = 5, m = 2en = 1), HOR (where O = 6, m = η = 1) , HSR (where S = 6, m = n = 1) or other compounds where H in X is acidic or the element X has another acidic group. Preferred examples for the compound of the formula RnXHm are hexanol, heptanol, octanol, dodecanol, hexadecanol, octadacanol, 2-aminomethylpropanol, hexylamine, dihexylamine, heptylamine, diheptylamine, octylamine, dioctylamine, nonylamine, dinonylamine, dodecylamine, dodecylamine, hexadecylamine, dihexadecylamine, octadecylamine, dioctadecylamine, di (2-ethylhexyl) amine, di (2-methoxyethyl) amine, 3- (2-aminoethylamino) propylamine, diisopropylamine, oleylamine, tallow, dicocoalkylamine and cocoalkylamine.

Preferred are compounds having a boiling point above 100 ° C, more preferably above 150 ° C.

For lower boiling or compound compounds of formula RnXHm with less reactivity, the reaction with the mineral may be performed under temperature and pressure in a closed reactor. The temperature and pressure range should be such that the least reactive formula compound RnXHm still remains liquid. Thus choosing the less reactive RnXHm compound defines the temperature and pressure range to be applied.

The reaction is carried out in a weight ratio of the mineral: Rn.XHm in the range 1: 1 to 1: 0.005, preferably 1: 0.2 to 1: 0.01, more preferably 1: 0.15 to 1: 0.02.

The reaction is carried out in a temperature range from 30 ° C to 300 ° C, preferably from 50 ° C to 200 ° C, more preferably from 80 ° to 180 ° C. The products of this mineral reaction / RnXHm are either cooled before being mixed with the polymer for isolation or can be directly prepared prior to use.

Preferably, before the mineral reacts with the compound of formula RnXHm, the mineral may be reacted with urea or DMSO (dimethyl sulfoxide).

The reaction time varies as a function of mineral: RnXHme ratio as a function of applied temperature. A higher temperature allows faster reaction than a lower temperature. A higher ratio of organic compound to mineral allows a greater likelihood of reaction than a lower ratio.

The advantage of the compounds formed is their thermal stability. Even at polymer extrusion temperatures or injection temperatures, as examples for polymer process parameters, these compounds do not decompose.

An additional advantage of the compounds of the present invention is that they are more hydrophobic than conventional onium clays, which can be proven in a modified Foster method.

To test whether the mineral is more or less hydrophilic, its behavior in a hydrophilic medium, such as water, ethanol or DM-SO, is evaluated.

To test whether the mineral is more or less hydrophobic, its behavior in a hydrophobic medium, such as an organic solvent, such as benzene, toluene, ethyl acetate or cyclohexane, is evaluated.

Water Test:

In a petri dish or other glassware, a small amount of the material to be tested is placed in the center. Then a few drops of water are placed on said material and the behavior of the drops of water is observed.

If the material tested is hydrophilic, water droplets quickly and easily penetrate the material tested.

If the material tested is hydrophobic, water droplets will not come into contact with the material. The surface tension of the water allows the water droplet to form a ball over the hydrophobic tested material to reduce the contact area. As the material is hydrophobic, it reduces the contact area with water droplets.

Testing with untreated material and modified material is recommended for better visualization of differences.

Usually grades can be given to test results:

0 = no penetration.1 = poor penetration,

2 = strong penetration,

3 = stronger penetration,

4 = very strong penetration.

Hydrophobic Organic Solvent Test:

In a petri dish or other glassware, a small amount of the material to be tested is placed in the center. Then a few drops of the hydrophobic organic solvent (such as xylene) are placed on top of said test material and the behavior of the solvent exhaust is observed.

If the material tested is hydrophobic, solvent drops quickly and easily penetrate the material to be tested.

If the material to be tested is hydrophilic, solvent drops will not come into contact with the material. The low surface tension of the solvent avoids solvent contact with the material.

Testing with untreated material and modified material is recommended for better visualization of differences.

Usually grades can be given to test results:

0 = very strong penetration,

1 = strong penetration,

2 = less strong penetration,

3 = low penetration,

4 = no penetration.

Conventional onium clays generally have a very hydrophobic behavior in the water test, which means that applying the water droplets to the conventional onium clay test results in a very contact area. little.

However, if the onium clay is subjected to the hydrophobic organic solvent test, the organic solvent will not penetrate. Thus, they perform very poorly on the hydrophobic organic solvent test, which means that they repel the solvent.

The mineral reaction / RnXHm reaction products of the present invention are more hydrophobic in the water test and demonstrate more hydrophobicity in the organic solvent compared to conventional onium clays. Thus, water is more repelled by the modified minerals of the present invention compared to conventional onium clay.

The highest hydrophobicity can be observed in the organic solvent test. The mineral reaction / RnXHm reaction products of the present invention dissolve in solvent while the onium clay clays are not soluble in the organic solvent.

While a conventional onium clay of the technical state receives a score of 2 to 3 in the water test, the reaction / RnXHm products of the present invention receive a score of 0 to 1 in the same test. And while a conventional state of the art onium clay receives a score of 3 to 4 in the organic solvent test, the mineral-giving / RnXHm products of the present invention receive a score of 0 to 1 of the same test.

Best results are achieved with a mineral having the following composition: (SiO2) x, (AI2O3) y, and other present metal oxides, such as Fe2Oa; and with a compound of the formula / RnXHm where R is greater than C 10 and X is O, such as dodecanol, hexadecanol; or mine-ral / RnXHm where R is greater than C-ιο and X is N, such as dodecylamine, hexadekylamine or octadecylamine.

A preferred embodiment is when the mineral has a fine particle size that passes through 250 mesh, preferably 325 mesh and more preferably 500 mesh.

Another preferred embodiment of the present invention is when the moisture content of the unmodified mineral is less than 10%, preferably less than 5%.

Another preferred embodiment of the present invention is when the unmodified mineral has an iron or titanium content (measured and calculated as oxides) of less than 3%.

Even better results are achieved if the mineral has the following composition: mineral / RnXHm where R is greater than C10 and X is O, such as dodecanol, hexadecanol, or mineral / RnXHm where R is greater than C-10 and X is N, as dodecylamine, hexadecylamine, octadecylamine.

The fields of application of the mineral-polymer composites of the present invention are wide. Non-limiting examples for such applications are in the packaging industry, engineering and, due to better performance, in applications directly or indirectly linked to the automotive industry. Other possible applications are for example in civil construction, such as plasticizers, foundry, ceramics (porous), pigment preparations, textiles and textile coloring, catalyst support, dermatology modifiers, polymer and paint miscibility, varnishes, coatings, nail polishes. In the automotive industry they are suitable for parts that must carry high loads and weights.

The compounds of the present invention may also be used in the presence of monomers which will be polymerized by known technologies. The compounds of the present invention may also be used in applications involving cables and wires, or as lubricants, agents for improving the mechanical strength of polymers, agents for reducing the problem of polymer fatigue, reducing or eliminating solvents in the product formulation. used as plasticizers, as hydrophobizing agents for polymers and allow less degradation.

The compounds of the present invention may be used in the polymerization of monomers. For example, they can be used in conjunction with typical catalysts such as those from Ziegler-Natta catalysis for polyethylene polymerization. They may also be used in the emulsion polymerization of the compounds of the present invention.

Examples

To illustrate the manner in which the present invention may be practiced, the following examples are provided in which all are understood to be parts by weight. The invention is best described with reference to the examples. The examples are to be understood merely as illustrative and not as limiting the scope of the invention. Starting materials for Poly (Vinyl Chloride) (PVC):

I.A) Polyolefin:

I.A1) Poly (vinyl chloride) (virgin), received by KARINAPLÁSTICO, São Paulo - SP, BRAZIL; melting temperature TM = 165 ° C (determined by DSC (differential scanning calorimetry) at 10 ° C min "1 (information received from supplier)).

I.A2) Recycled poly (vinyl chloride) received by DUBLATEClnd. and Com. de Calçados Ltda., Juazeiro do Norte - CE1 BRAZIL.

Recycled PVC is a mixture of various types, each fraction at least once recycled; melting temperature TM = 155 ° C (determined by DSC (differential scanning calorimetry) at 10 ° C min "1 (information received from supplier)).

I.B) Lamellar clay:

I.B1) 500 g of Bofe Juá da Bentonisa S.A. clay, João Pessoa -PB, Brazil were mixed with 85.7 g of hexadecanol and 500 mL of hexane. The mixture is heated in an open reactor at 120 ° C for 2 hours. The product is filtered and the solid residue is washed twice with toluene and dried.

I.B2) 74.5 g of vermiculite from Soleminas S.A., Soledade - PB, Brazil, which was previously expanded and milled with 200 mesh, was mixed with 40.1 g of hexadecylamine. The mixture is heated in an open reactor at 120 ° C for 2 hours. The product is cooled and can be used.

I.B3) 260 g of Chocolate Clay A Lajes 200 mesh of BentonisaS.A., Joao Pessoa - PB, Brazil were mixed with 20.87 g of hexadecylamine and 300 ml of hexanol. The mixture is heated in an open reactor at 120 ° C for 2 hours. The product is filtered and the solid residue is washed twice with toluene and dried.

I.B4) 453 g of kaolin from Soleminas S.A., Soledade - PB, Brazil, were mixed with 41.9 g of hexadecylamine and 300 ml of hexanol. The mixture is heated in an open reactor at 120 ° C for 2 hours. The product is filtered and the solid residue is washed twice with toluene and dried.

I.B5) Kaolin, Soleminas S.A., Soledade - PB, Brazil.Ι.Β6) Expanded vermiculite is ground # 200, Soleminas S.A., So-ledade - PB, Brazil.

I.C) Other:

I.C1) Calcium carbonate 200 mesh, Soleminas S.A., Soledade-PB, Brazil.

I.C2) Silica 200 mesh, Soleminas S.A., Soledade - PB, Brazil.Preparation of composites with high stiffness (Comparative Experiment 1 and 5e Examples 2 to 4 and 6 to 8):

The same preparation was used for all examples. The polymer (and, depending on the examples, the additive (s), fillers and the other ingredients) were placed in a binder. In this mixing machine, the polymer (and, depending on the examples, the additive (s)) were kept at 1,000 rpm for 3 minutes, a slight temperature increase was observed. After three minutes, the mixture was removed from the binder, the sample was placed directly into the feed zone of an injector.

The injector was equipped with a 1.5 m long extrusion screw (T = 175 ° C, t = 3 minutes, 200 rpm), with heating maintained at 185 ° C from King Steel, Taipeh - Taiwan. The composition of various polyolefin composite materials is shown in Table 1.1 and Table I.2. The polymeric mass is injected into steel forms where the formation of the composite is completed in about 5 minutes. Then, the formed article obtained is evaluated by its appearance in the cut (appearance coming out of shape = appearance in Table I.3).

Good appearance indicates a homogeneous shape with the bubbles in a homogeneous distribution. Poor appearance indicates that the bubbles are irregular, but in a homogeneous distribution. Very poor appearance indicates that the bubbles formed are irregular and in a nonhomogeneous distribution.

The only difference is the composition of the sample.

The hardness can be determined by pressing the finger on the surface of the formed article and the force required to achieve a change is evaluated. This method is subjective. More objective is the determination of the hardness in ASTM 2240. The absorption of organic solvent (ethyl acetate (AcOEt) or xylene) and water is made as follows: from the specimen is cut a piece of about 1 cm χ 1 cm χ height of the body and fully immersed for 1 and 2 hours in the solvent / liquid. After 1h, excess solvent / liquid deposited on the outside of the specimen is dried with paper.

Then the body is weighed and immersed for a second hour where at the end the same procedure is repeated. The initial deprovable body weight is used for comparison with weights after 1 and 2 hours of immersion. The fatigue test was performed at PENALTY S.A., Bayeux - PB unit, Brazil. The specimen is fixed to the apparatus after applying three thin needles to injure the surface. After 50,000 cycles the results were evaluated:

Broken = the bruise grew and the body broke.

Minor signs of defect = the wound of the three needles grew into a visible stripe.

Without any sign of defect = beyond the injury of the three needles there is no change after 50,000 cycles.

Table 1.1

<table> table see original document page 27 </column> </row> <table> <table> table see original document page 28 </column> </row> <table>

Table 1.2

<table> table see original document page 28 </column> </row> <table>

Table 1.3

<table> table see original document page 28 </column> </row> <table> <table> table see original document page 29 </column> </row> <table>

II. Starting materials for Polyethylene (PE):

II.A) Polyolefin:

II.A1) High-density (virgin) homopolymer polyethylene HF-0147, from BRASKEM, Porto Alegre - RS, BRAZIL; melting temperature TM = 195 ° C (determined by DSC (differential scanning calorimetry) at 10 ° C min "1 (information received from supplier)) was mixed with low density (virgin) homopolymer polyethylene LL-118, received byBRASKEM, Porto Alegre - RS, BRAZIL; melting temperature TM = 190 ° C determined by DSC (differential scanning calorimetry) at 10 ° C min'1 (information received by the supplier)) at a ratio of 84: 16.

II.B) Lamellar clay:

II.B1) RAVA2 Starting Material:

Kaolin of Soleminas S.A., Soledade - PB, Brazil.

II.B2) RAVA3 Starting Material:

Chocolate A Lajes # 200 from Bentonisa S.A., João Pessoa - PB1Brasil.

II.B3) RAVA7 Starting Material:

A typical sodium montmorillonite was transformed by the well-known prior art method into an onium clay via an ammonium salt having a carbon chain group larger than C16. The process was made with technology known to Bentonisa SA João Pes -soa - PB / Brazil (see Silva, Adriana Almeida, Obtaining Organic Clay / Rubber Nanocomposites, Federal University of Campina Gran-de, Center for Science and Technology, Graduate Program in Science and Materials Engineering, Campus I - Campina Grande - Paraíba / Brazil, 118pp., September - 2006).

II.B4) RAVA8 Starting Material:

The same montmorillonite from II.B3 was transformed into an onium clay by the well-known prior art method using an ammonium salt having two carbon chain groups larger than C1-6.

The process was carried out using known technology at Bentonisa SA João Pes-soa - PB / Brazil (see Silva, Adriana Almeida, Obtaining Clay / Rubber Organic Nanocomposites, Federal University of Campina Gran-de, Center for Science and Technology, Post Program Degree in Science and Materials Engineering, Campus I - Campina Grande - Paraíba / Brazil, 118pp., September - 2006).

II.B5) RAVA9 Starting Material:

510 g of kaolin from Soleminas S.A., Soledade - PB, Brazil, was mixed with 51.2 g of hexadecanol. The mixture is heated in an open reactor at 180 ° C for 2 hours. The product repels water better than II.B3 and II.B4 asargils, and dissolves in xylene while II.B3 and II.B4 clays do not dissolve in xylene.

II.B6) RAVA10 Starting Material:

585 g of kaolin from Soleminas S.A., Soledade - PB, Brazil, were mixed with 58.4 g of hexadecylamine. The mixture is heated in an open reactor at 180 ° C for 2 hours under stirring. The product repels water better than the II.B3 and II.B4 clays, and dissolves in xylene while the II.B3 and II.B4 asargils do not dissolve in xylene.

II.B7) RAVA11 Starting Material:

570 g of Chocolate Clay A Lajes 200 mesh of Bentonisa S.A., Boa Vista - PB, Brazil, were mixed with 57.2 g of hexadecanol. The mixture is heated in an open reactor at 180 ° C for 2 hours under stirring. The product repels water better than II.B3 and II.B4 clays, and dissolves xylene while II.B3 and II.B4 clays do not dissolve in xylene.

II.B8) RAVA12 Starting Material:

1010 g of Chocolate Clay The Laenton 200 mesh of BentonisaS.A., Boa Vista - PB, Brazil, were mixed with 101.4 g of hexadecylamine. The mixture is heated in an open reactor at 180 ° C for 2 hours under agitation. The product repels water better than II.B3 and II.B4 clays, and dissolves in xylene while II.B3 and II.B4 clays do not dissolve xylene.

Preparation of high stiff composites (Comparative Experiments 1 to 5 (RAVA 1-3, 7 + 8) and Examples 6 to 9):

The same preparation procedure was used for all examples. The polymer (and, depending on the examples, additive (s), filler and other ingredients) were premixed and then placed directly into the feed zone of an injector to produce polyethylene sheets.

The machine was equipped with a 1.5 m long extrusion screw (T = 195 ° C, t = 3 min, 200 rpm) in which the heating unit was maintained at 185 ° C of King Steel, Taiwan . The composition of the various polyolefin-based composite materials is shown in tables 11.1 and table II.2.

The only difference is the composition of the sample.

The mechanical properties of each composite at ambient temperature are shown in table 11.1.

The absorption of the organic ethyl acetate solvent (AcOEt) is as follows: from the film a piece of about 1cm χ 1cm is cut and fully immersed for 1 and 2 hours in the solvent. After 1h the excess of the sun deposited outside the specimen is dried with paper. Then the body is weighed and immersed for a second hour where in the end the same procedure is repeated. The initial specimen weight is used to compare with the weights after 1 and 2 hours of immersion.

Mechanical tests were performed at TERPHANE S.A., Cabode Santo Agostinho-PE, Brazil. Based on ASTM D-882, tensile strength, modulus of elasticity, tension at 5% strength and elongation were determined.

Table 11.1 Resistance, modulus of elasticity, tension and elongation based on ASTM D-882.

<table> table see original document page 31 </column> </row> <table> <table> table see original document page 32 </column> </row> <table>

Table 11.1 (cont.)

<table> table see original document page 32 </column> </row> <table>

As can be seen the composites of the present invention reduce solvent absorption better than prior art compounds.

III. Starting materials for styrene butadiene copolymer (SBR):

III.A) Polyolefin:

III.A1) A typical formulation of a 32% SBR1 product recycled from LANXESS SBR1 based Cabo de Santo Agostinho -PE, BRAZIL, with other typical raw materials such as zinc oxide, ex-sweeper, conventional kaolin, and others, were mixed with and without the compound of III.Β. in a BANBURY mixer for 5 minutes. Then the mixture is turned into leaves and allowed to stand for 24 hours. Then, by adding other typical additives and cutting the sheet, the specimen is placed in a press for 5 minutes at 160 ° C 1 MPa compression. The vulcanized SBR body is evaluated. The formulation, the equipment and the production of the specimens were performed at the Brazilian Company of Sandália S.A., Carpina - PE, Brazil.

III.B) Lamellar clay:

III.B1) 855 g of kaolin from Soleminas S.A., João Pessoa - PB1Brasil, were mixed with 42.5 g of hexadecylamine. The mixture was heated in an open reactor at 180 ° C for 2 hours under stirring. The product repeats water better than the clays of II.B3 and II.B4, and dissolves in xylene whereas the clays of II.B3 and II.B4 do not dissolve in xylene. Preparation of high stiff composites (Comparative Experiments 1 and 2 and Examples 3 and 4):

The same preparation procedure was used for all examples. The polymer (and, depending on the examples, additive (s), filler and other ingredients) were placed in the BANBURY type mixer as described above. In this apparatus, the polymer (and, depending on the examples, additive (s), fillers and other ingredients)) was mixed for 5 minutes.

The temperature increase in the mixture is greater if the compound of the present invention is not present. After five minutes, the mixture goes into a cylinder that turns the dough into leaves. The leaves are cut into strips of 30 cm χ 80 cm and have a thickness of 0.75 cm. The cut leaves are allowed to stand for 24 hours at room temperature. The sheets are then cut to the desired size to fit the shape of the press and can be mixed with typical additives and the mixture is placed in the press as described above.

The composition of the various SBR-based composite materials is shown in Table III.1. The formed article obtained is evaluated by its appearance in the cut (appearance coming out of shape = appearance in Table III.1). Good appearance indicates a homogeneous shape with the bubbles in a homogeneous distribution. Poor appearance indicates that the bubbles are irregular, but in a homogeneous distribution. Very bad appearance indicates that the bubbles formed are irregular, and in a nonhomogeneous distribution.

The only difference is the composition of the sample.

The mechanical properties of each composite at ambient temperature are shown in Table III.1. Hardness determination was made based on measurement ASTM 2240. The absorption of xylene organic solvent and water is made as follows: a piece of fence specimen is cut 1 cm χ 1 cm χ body height, which is completely immersed by 1 and 2 hours in solvent / liquid. After 1h, excess solvent / liquid deposited on the outside of the specimen is dried with paper. Then the body is weighed and immersed for a second hour where, at the end, the same procedure is repeated. The initial specimen weight is used to compare with the weights after 1 and 2 hours of immersion.

Table III.1

<table> table see original document page 34 </column> </row> <table>

As can be seen, the composites of the present invention retain mechanical properties, however, as the oil-containing formulation has been maintained, and as the modified minerals of the present invention as a fluxing agent, hardness is slightly reduced and solvent absorption has increased. Water absorption is reduced in the presence of the modified minerals of the present invention.

Claims (33)

1. Composite, characterized in that it comprises: a) a mineral containing amphoteric or acidic groups; and b) at least one hydrophobic polymer, wherein the mineral is reacted with at least one compound of the formula RnXHm, wherein: X is O, N or S, the sum of the group number of element X in the Periodic Table Elements, of η and of m is equal to 8; eR is an alkyl radical of 3 to 50 carbon atoms, linear or branched, substituted or unsubstituted, aliphatic, cyclic or aromatic, and wherein the weight ratio of mineral to hydrophobic polymer is 10:90 to 0, 1: 99.9, preferably from 7:93 to 1:99, more preferably from 2.5: 97.5 to 1:99. Composite according to claim 1, characterized in that the mineral is selected from the group consisting of silicates, carbonates and metal oxides. Composite according to claim 2, characterized in that the silicate is crystalline silicate containing galleries (clays). Composite according to any one of claims 1 to 3, characterized in that the mineral is selected from the group consisting of minerals of smectite, montmorillonite, kaolinite, hectorite, fluorhectorite, hydroxyl hectorite, saponite, laponite, and same combinations. Composite according to claim 4, characterized in that the mineral gallery contains at least one charge balance cation selected from the group consisting of sodium ions, potassium ions, lithium ions, calcium and magnesium ions. Composite according to claim 4 or 5, characterized in that the mineral is smectite or kaolinite. Composite according to claim 1, characterized in that R is selected from the group consisting of hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, hepta-decyl, octadecyl, nonadecyl, 2. -methylhexyl, 3-methylhexyl, 2-methylheptyl, -3-methylheptyl, 2-methyloctyl, 3-methyloctyl, 4-methyloctyl, 2-ethylhexyl, 2-ethylheptyl, 3- ethyloctyl, benzyl, methylbenzyl, ethylbenzyl, toluyl, xylene, nonylphenyl, cyclohexyl, cycloheptyl and cyclooctyl. A compound according to claim 1, characterized in that the compound of the formula RnXHm is selected from the group consisting of hexanol, heptanol, octanol, dodecanol, hexadecanol, octadacanol, 2-aminomethylpropanol, hexylamine, dihexylamine, heptylamine, diheptylamine, octylamine, dioctylamine, nonylamine, dinonylamine, dodecylamine, didodecylamine, hexadecylamine, dihexadecylamine, octadecylamine, dioctadecylamine, di (2-ethylhexyl) -amine, di (2-methoxyethyl) -amine, 3- (2-aminoethylamino) propylamine, diisopropylamine, oleylamine, desebo alkylamine, dicocoalkylamine and cocoalkylamine. Composite according to any one of claims 1 to 8, characterized in that the polymer is a thermoplastic polymer or a thermosetting polymer. Composite according to claim 9, characterized in that the polymer is a thermoplastic polymer. Composite according to Claim 9, characterized in that the polymer is selected from the group consisting of vinyl empolymers, polyalkylene oxides, polyesters, vinylene polymers, fluorine polymers, polysiloxanes, polyphenylene sulfides, polyacids, polycarbonates, polysulfones, polyethersulfones, phenolic resins, epoxy resins, alkyd resins, furan resins, urea resins, melamine resins, polyurethane resins and aniline resins. Composite according to claim 9, characterized in that the polymer is based on ethylene monomers, propylene monomers, styrene monomers, butadiene monomers, butadiene and styrene monomers, vinyl chloride monomers or monomers. amides. Composite according to claim 12, characterized in that the polymer is polyethylene, polypropylene, polystyrene or polyacrylate. Composite according to any one of claims 1 to 13, characterized in that the polymer is a recycled material or a mixture of virgin and recycled polymers, wherein the polymer content is 1 to 50% by weight; of the total fraction of the polymer in the composite. Composite according to claim 14, characterized in that the virgin polymer content is less than 10% by weight. Composite according to claim 14 or 15, characterized in that virgin and recycled polymers belong to the same family of polymers. Composite according to any one of claims 1 to 16, characterized in that the mineral has an iron or titanium content (calculated as oxides) of less than 3%. Composite according to any one of claims 1 to 17, characterized in that the at least one hydrophobic polymer is a mixture of at least two different polymers for use in polymerizing the monomer units. Composite according to claim 18, characterized in that the mixture comprises SBR (styrene-butadiene copolymer), PA (polyamide), PP (polypropylene), PE (polyethylene), PVC po-li (vinyl chloride) or immiscible polymers. 20. Process for the production of a modified mineral, characterized in that it comprises the steps of: a. provide a mineral containing amphoteric or acidic groups, b. reacting the mineral from step a) with at least one compound of formula RnXHm, wherein: X is O, N or S, the sum of the group number of element X in the Periodic Table Elements, of η and m is equal to 8; eR is an aliphatic, cyclic or aromatic linear or branched, substituted or unsubstituted alkyl radical of 3 to 50 carbon atoms, wherein step b) is carried out in the temperature range of 30 ° C to 300 ° C and with vigorous agitation; thus forming a low molecular weight component and the modified mineral; ec. eliminating the low molecular weight component formed in step b). Process according to Claim 20, characterized in that the mineral is selected from the group consisting of silicates, carbonates and metal oxides. Process according to Claim 21, characterized in that the silicates are crystalline silicates containing galleries (clays). Process for producing a composite as defined in any one of claims 1 to 19, characterized in that it comprises the steps of: a. provide a mineral containing amphoteric or acidic groups, b. reacting the mineral from step a) with at least one compound of formula RnXHm, wherein: X is O, N or S, the sum of the group number of element X in the Periodic Table Elements, of η and m is equal to 8; eR is an aliphatic, cyclic or aromatic linear or branched, substituted or unsubstituted alkyl radical of 3 to 50 carbon atoms, wherein step b) is carried out in the temperature range of 30 ° C to 300 ° C and with vigorous agitation; thus forming a low molecular weight component and the modified mineral c. eliminating the low molecular weight component formed in step b); ed. modifying the above described mineral formed in step b) to make at least one hydrophobic polymer, thereby forming the composite. Process according to claim 23, characterized in that step d) is carried out under vigorous mixing and under conditions of temperature, pressure and / or cross-linking which allow a workability of the chosen polymer. Process according to Claim 23, characterized in that step d) is performed at a temperature above the polymer melt temperature for polymer systems which may be extruded or injected. Process according to any one of claims 23 to 25, characterized in that the mineral passes through a 200 mesh screen, preferably through a 325 mesh screen, more preferably through a mesh screen. 500, before reacting with the compound of formula RnXHm. A process according to any one of claims 23 to 26, further comprising the step of mixing the mineral and polymer in a mixer, followed by a 5 minute to 24 hour rest. Process according to any one of claims 23 to 27, characterized in that it comprises integrating the nopolymer mineral through an extrusion process. Product, characterized in that it comprises the purpose as defined in any one of claims 1 to 19 or is produced by the process as defined in any one of claims 23 to 28. A product according to claim 29, further comprising additives, fillers, reinforcing materials, flame retardants, foaming agents, stabilizers, anti-blocking agents, acid scavengers, antistatic agents, promoting agents. flow, dyes or pigments. Product according to Claim 29 or 30, characterized in that it is a cable or a wire. 32. Use of a composite as defined in any one of claims 1 to 19, characterized in that it is in packaging, engineering applications, the automobile industry, mold production, civil construction, inks, electronics, or in textiles. Use of the mineral compound / RnXHm as defined in any one of claims 1 to 18, characterized in that it is a plasticizer, as a rheology modifier, for the absorption of oils as an agent for improving the miscibility of systems. little miscible or immiscible, to improve fatigue strength, or to improve polymer flow behavior.