CH615896A5 - Process for preparing a silicate-containing inorganic product modified with an organosilane - Google Patents

Abstract

The surface of a water-insoluble inorganic material (metal carbonate and/or sulphate) is brought into contact, in the presence of water, with a precipitated insoluble metal silicate, the silicate at the surface of the inorganic material is dried and is treated with a bonding organosilane. The products obtained can be used as filler for the reinforcement or pigmentation of synthetic polymer composites to which these products impart better mechanical characteristics.

Description

The present invention relates to new mineral materials treated with metal silicates, which are receptive to silane binding agents. More particularly, the present invention relates to mineral fillers treated with metal silicates, a process for producing these fillers and composite polymer compositions containing these treated fillers and silane bonding agents, as well as mineral fillers treated with silicate of metal and modified with silane and composite polymer compositions containing these mineral fillers treated with metal silicate and modified with silane.

The use of finely divided fibrous and particulate mineral materials, commonly referred to as mineral fillers or mineral pigments, to incorporate them into rubbers, resins, paints, inks and other substances to form composite compositions, is well known in practice. For example, the use of non-siliceous mineral fillers, for example natural and synthetic calcium carbonates and partially siliceous pigments obtained by synthesis and mixture in co-precipitation, for example calcium carbonate / silica and calcium carbonate / silicate of metal, as fillers in polymer composites / fillers, is well known, as shown, for example, in British Patent No. 838903 and in United States Patent No. 2928802, No. 3152001 and N ° 3290165. In addition, it is known that certain entirely siliceous fillers, for example fillers of natural and synthetic silicas and fillers of metal silicates, when they are used as fillers in polymer composites / fillers, respond to the action organo-silanic silver bonds with production of better properties of the cured composite, as can be seen, for example, thanks to United States patents No. 2665264, No. 2744879, No. 28318 28, No. 2831829 and No. 2897173. However, natural and synthetic calcium carbonates and other non-siliceous mineral fillers show, in the presence of organosilane binding agents, no significant or useful response for improving the properties of composites of finished polymers. Since certain non-siliceous mineral fillers, in particular calcium carbonate, are among the most abundant, economical and most widely used particulate fillers in polymer / filler composites, their lack of response to the action of organosilane agents. bonding constituted a significant technological disadvantage for the development of better compositions of polymer composites / fillers.

A process has just been discovered for preparing a silicate mineral product modified by an organosilane binding agent. This product, used as a filler in polymer composites, gives better properties to finished composites.

More particularly, the subject of the present invention is a process according to which: a) the surface of a mineral material insoluble in water, chosen from metal carbonates, sulfates of metals and their mixtures, with a silicate insoluble in water, precipitated and not dried, b) this metal silicate is dried on the mineral matter insoluble in water, and c) the product is brought into contact with an organosilane agent link.

The mineral materials insoluble in water, which are used in the present invention, are chosen from carbonates and / or sulphates of metals, the metal of which is chosen from barium, beryllium, calcium, magnesium, strontium, zinc and their mixtures. Such mineral materials are commonly identified, for industrial use and in practice, by their chemical name and by their mineralogical name and they include, for example, barium carbonates (witherites), barium sulfates (barytes, fixed white ), beryllium carbonates, calcium carbonates (whites, calcites, marbles, lime), calcium sulfates (gypsum, anhydrites, alabaster), magnesium and calcium carbonates (dolomites), magnesium carbonates (magnesites ), strontium carbonates (strontianites), zinc carbonates (smithsonites), as well as the precipitated salts of these carbonates and sulfates, for example precipitated calcium carbonates and sulfates, precipitated barium sulfates and carbonates, precipitated zinc, precipitated magnesium carbonates, etc. Of course, it should be understood that in addition to the use of a single mineral material at a time, insoluble in water, it is possible, if desired, to use mixtures of two or more different mineral materials, insoluble in water. In addition, the particle size and shape of the water-insoluble mineral matter used is not fundamental, and is dictated primarily

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mainly by the final use only of the desired final treated mineral product (for example, one could treat a marble slab with the metal silicate insoluble in water, according to the present invention, if one wishes to fix or stick silane bonding agents to marble). Since the main end use of the mineral products treated with metal silicate according to the present invention is that of fillers or pigments in polymer / filler composites, it is preferred to use the initial mineral material, insoluble in water, in a form classic particulate. Many qualities of the various kinds of water-insoluble particulate mineral matter mentioned above are listed in "Materials and Compounding Ingredients for Rubber", Bill Publications, New York, New York, 1968 (materials and ingredients for forming rubber). Mineral materials insoluble in water, natural or produced by synthesis, can be used here. The preferred mineral materials are natural and synthetic metal carbonates, and natural calcium carbonates are especially preferred. Of course, it is clear from the above description, and it should be understood, that the mineral materials insoluble in water, natural and synthetic, which are used in the present invention are non-siliceous mineral materials, and they should not be confused with pigments or structural fillers which are mixed coprecipitation products obtained by synthesis, partially siliceous and composed of silica and non-siliceous constituents coprecipitated. However, it should also be understood that the mineral materials used in the present invention may contain small amounts of mineral siliceous substances associated as impurities, which distinguishes them from mineral siliceous substances added deliberately and intentionally.

The water-insoluble metal silicates, which are the salts usable in the present invention, include any metal salt of water-insoluble, precipitated, water-insoluble silicic acid, as well as their mixtures, in which the metal is chosen from aluminum, barium, beryllium, cadmium, calcium, cobalt, copper, iron, lead, lithium, magnesium, manganese, mercury, nickel, silver, strontium, tin, zinc, zirconium and rare earth metals having atomic numbers between 57 and 71, inclusive.

These silicic acid salts and the processes for their preparation are well known in the art; they are conventionally precipitated from an aqueous composition of silicate ions and a water-soluble metal salt. The water-soluble metal salt used to prepare the silicic acid salts can be any metal salt having a solubility of at least 0.1% by weight in water at 25 ° C , the metal can be chosen from aluminum, barium, beryllium, cadmium, calcium, cobalt, copper, iron, lead, lithium, magnesium, manganese, mercury, nickel, silver, strontium, tin, zinc, zirconium and rare earth metals having atomic numbers between 57 and 71, inclusive.

Of course, it should be understood that the expression water-soluble metal salt includes single salts, double salts and mixtures of such salts; these salts can contain any anion or any combination of anions forming a metal salt having the above-mentioned solubility, such as chloride, bromide, iodide, nitrate, nitrite, sulfate, sulfite, thiosulfate, thiosulfite, carbonate ions , bicarbonate, formate, acetate, glycolate, alkylsulfonate, cyanate, cyanide, thiocyanate, chlorate, bromate, iodate, hydroxide, etc. The preferred metals are barium, calcium and zinc, while the preferred anions are chloride, nitrate and sulfate ions. Examples illustrating such metal salts include barium chloride, barium nitrate, calcium chloride, calcium nitrate, zinc chloride, zinc nitrate and zinc sulfate.

Water-soluble salts of metals are normally used in the form of solutions or dispersions in solvents consisting of water or in mixtures of water and in miscible proportions of organic solvents such as, for example, methanol, ethanol , propanol, ethylene glycol, glycerin, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dimethyl sulfoxide, acetone, dimethylformamide, dimethylacetamide, trimethylamine, phosphoric hexamethylamide, etc. Such metal salts can be used alone, or, if desired, in the form of mixtures of two or more different salts. In addition, such water-soluble solutions or dispersions may contain acids such as hydrochloric, sulfuric and nitric acids, etc., in amounts necessary to meet a desired stoichiometry for the formation of the water-insoluble metal silicate. which it is desired to use in the present invention.

Silicate ions, in the above aqueous compositions used for the preparation of water-insoluble metal silicates, can include monosilicate ions as well as polysilicate ions and mixtures thereof, and these ions can come from any silicate solution , that is to say a liquid mixture of a solvent and of one or more silicon compounds capable of providing monosilicate or polysilicate anions such as, for example, monomeric and polymeric silicic acids; alkali metal salts of monomeric and polymeric silicic acids, except lithium salts; ammonium, guanidinium and hydrazinium (organosubstituted) salts of monomeric and polymeric silicic acids; lower alkyl, alkoxyalkyl, alkyl-aminoalkyl and dialkylaminoxy esters of monomeric and polymeric silicic acids; acylates of lower alkyl and alkoxyalkylic carboxylic acids and of monomeric and polymeric silicic acids; tetrakis (dialkylamino) silanes and their partially hydrolyzed and condensed derivatives, etc. The solvent for these silicate solutions consists of water or water-miscible organic solvents, as mentioned above, or mixtures thereof. A single source of the silicate ions can be used but, if desired, mixtures of two or more different sources of the silicate ions can also be used. In addition, if desired, such sources of silicate ions may contain bases such as sodium, potassium, ammonium and substituted ammonium hydroxides, in amounts necessary to meet a desired stoichiometry for silicate formation of water insoluble metal which it is desired to use in the present invention.

As indicated above, in the present invention, the water-insoluble metal silicates are used in the form of precipitated and undried salts, that is to say that these salts have not been completely dried after their initial formation, and they are used when they still contain at least the humidity they had during their precipitation. Preferably, it is desired to use the water-insoluble metal silicates in the form of freshly precipitated, highly hydrated and incompletely condensed salts, since the time interval between the formation of the water-insoluble metal silicate and its contact with mineral matter insoluble in water has an influence on obtaining the best results that one wishes to have. For example, it has been found that when suspending precipitated metal silicate, which has been kept in dilute aqueous suspension for various time intervals, with a mineral material insoluble in water, it is found that the mineral product treated with silicate, after its elaboration treatment, responds to silane binding agents. However, when the time interval between the formation of the water-insoluble metal silicate and its contact with the water-insoluble mineral material is increased, the response of the mineral material treated with the silicate to with regard to silane binding agents decreases. In an extreme case, when a water insoluble metal silicate, completely dried beforehand and condensed, has been redispersed in water and it has been suspended with a mineral matter insoluble in water, it was found that the mineral product thus treated and recovered did not show any response to the action of the silane binding agent. So in order to guarantee obtaining

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for best results, it is especially preferred to prepare the mineral products treated with silicate according to the present invention by precipitation of the metal silicate insoluble in water in the presence of the mineral matter insoluble in the water to be treated. It is less preferred, but this still remains within the scope of the present invention, to bring the mineral material insoluble in water into contact with the silicate of metal insoluble in water and not dried, this contact being killed at the end. a short period of time after precipitation of the silicate (and the shorter the time interval after precipitation, the better the results obtained).

The metal silicate treated mineral products of the present invention can be prepared, which may respond to the action of silane binding agents, in any manner involving contact with the surface of the mineral material insoluble in water in the presence of water with a metal silicate insoluble in water, precipitated and not dried, and then drying the mineral product thus treated with silicate.

Here are examples illustrating such processes:

A) The solution of the water-soluble metal salt and the water-soluble silicate solution are added at the same time as or successively to an aqueous suspension, subjected to stirring, of the mineral matter insoluble in the water to be treated, in order to form, in the presence mineral matter, metal silicate insoluble in water. The mineral product treated with the silicate can then be dried and recovered by any conventional method desired.

B) First, a dilute aqueous solution of the water-insoluble metal silicate is formed by mixing a water-soluble silicate solution and a water-soluble metal salt and then, operating in a short period of time and without drying the silicate. of insoluble metal thus formed, the suspension of the water insoluble metal silicate is brought into contact with the surface of the mineral material insoluble in the water to be treated. The mineral product treated with the silicate can then be dried and recovered by any conventional method desired.

C) The mineral product treated with silicate can also be prepared by introducing, using at least one pump, streams of an aqueous suspension of the mineral matter insoluble in the water to be treated, a solution of a water-soluble metal salt and a water-soluble silicate solution in a highly turbulent zone, such as a mixing tee, and by removing a suspension of the mineral product treated with the silicate and which can then be dried and recovered by any what a classic process wanted.

D) It is possible to spray or spray aqueous solutions of the water-soluble metal salt and the water-soluble silicate, in atomized form, simultaneously or successively, onto a stirred mass of the mineral matter insoluble in the water to be treated. The mineral product treated with the silicate can then be dried and recovered, in any conventional manner desired.

Preferably, it is desired to precipitate the metal silicate insoluble in water while it is in contact with the surface of the mineral material insoluble in the water to be treated, in particular by method A) indicated above. For example, to a stirred suspension of particulate calcium carbonate in water, aqueous solutions of sodium silicate and sodium chloride are added in such proportions that a small amount of silicate is precipitated. of calcium insoluble in water. The mineral product (calcium carbonate) treated with calcium silicate is then washed, filtered, dried and recovered as desired, and it can be used as explained more fully below.

During the formation of the mineral products treated with metal silicate according to the present invention, by any of the methods described above, the operating factors of initial concentration of the mineral product, of temperature, of concentrations of the solutions of the compounds before reaction and addition rates are not fundamental factors, although some practical choices can be made, as described below.

The initial concentrations of the mineral products are not fundamental and they can be located, at the beginning of a preparation,

between 100% by weight, that is to say an undiluted dry mineral matter, as in the case of spray coating processes, up to any desirable level as in the case of processes operating in suspension. In suspension preparations, one usually begins with the concentrations of mineral products at the highest levels allowing adequate agitation by the equipment used.

The temperature used during the formation of mineral products treated with metal silicate is not known to be fundamental, and can be maintained at any point between the freezing point and the boiling point of aqueous solvent. For the sake of convenience and economy, the treatment procedure is usually carried out under normal ambient conditions, that is to say between about 18 and 30 ° C. Normal atmospheric pressure is also normally used. However, if desired, higher or lower pressures can be used.

. The concentrations of the water soluble metal salt and the water soluble silicate reacted in their solutions are not fundamental and are simply chosen to form stable solutions or dispersions at levels suitable for the particular process of preparation that we use. For example, in most suspension preparations, concentrations of about 10% by weight are convenient, although higher or lower levels of proportions can be used. Furthermore, in a treatment of the mineral material by spray projection, higher concentrations of the compound to react are useful to avoid flocculation of the powder subjected to stirring.

The rates of addition of the solutions of the compounds to be reacted are not fundamental either, but localized zones of too high concentration in the reaction mass should be avoided. Thus, in batch suspension processes, it is convenient to add a solution of compound to react fairly quickly to the suspension (usually, but not necessarily, the silicate solution) and to control the rate of formation of the insoluble metal silicate in water by adding the solution of the other compound to react in a period of time between a few minutes and several hours, or even in a longer period of time. On the contrary, when very high agitation rates are used, as in tees for continuous mixing, it is possible to add at the same time, in a fraction of a second, the whole quantities of the compounds which have to react and which are necessary for unitary entity of mineral product.

As indicated above, it is preferred that the operating factor of the process described as being the time until contact, that is to say the time interval between the formation of the metal silicate insoluble in water and its contact with the mineral product insoluble in water, be as short as possible to obtain the best results that one wishes to have.

The procedures used to dry and recover the mineral material insoluble in water, treated with metal silicate, are not fundamental and one can use, as desired, any conventional process such as drying by atomization, abandoning the mineral matter so that it dries at room temperature, drying in an oven or an oven, etc. Normally, the mineral material treated with metal silicate is washed with water and is separated from the reaction solution by filtration, for example, then it is dried in an oven or in an oven. Of course, it should be understood that the mineral product treated with metal silicate may still contain a little moisture even after it has dried, but it is generally preferred to dry the mineral material treated with metal silicate to a weight. essentially constant at temperatures above about 100 ° C or at least up to a moisture content at which the mineral material treated with metal silicate is no longer wet to the touch. It should also be understood that, if the mineral to be treated is used in the form of a filler or a particulate pigment, the mineral product can easily be returned

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treated with metal silicate to its particulate form by any suitable method of grinding, if the product has been obtained in the form of a cake.

The chemical compositions of the water-insoluble metal silicates used in the present invention can also be conveniently expressed in terms of the ratio of metal oxide to Si02, for example Mx0y / Si02, where M is the metal and x and y are normal valences of combination of oxide and metal ions, respectively, as explained for example in "Dana Mineralogy" by Dana, 18th edition, John Wiley, New York, 1971, p. 202. Thus, the ratio between the metal oxides and the silicate ions in the water-insoluble metal silicates is equal to the number of moles of MxOy divided by the number of moles of SiO2 in the salt. The ratio of metal oxide to SÌO2 in the water-insoluble metal silicates used in the present invention can be between about 0.1 and 4 or higher, if desired, however which is preferred, for metal oxide, a ratio of less than about 3.1.

Obviously, the amount of water-insoluble metal silicate used in the present invention need only be the amount sufficient to make the starting mineral material insoluble in water and untreated capable of responding or reacting. to the action of silane binding agents, which, of course, will depend to a large extent on the intended end use for the inorganic product treated with silicate. Since the mineral product treated with water-insoluble metal silicate is preferred to be used in particulate form, the water-insoluble metal silicate can generally be precipitated and used in amounts of between 0.1 and 20 parts by weight per 100 parts by weight of the starting mineral material. Preferably, the amount of water-insoluble metal silicate that is used is between about 0.3 and about 10 parts by weight per 100 parts by weight of the starting mineral material.

The amount of water present need only be sufficient to dissolve the water-soluble metal salt and the silicate ion to be reacted, such as when spraying solutions of the water-soluble metal salt and solutions of the silicate ion onto the surface of the mineral matter insoluble in the water being treated. However, for the sake of convenience and ease of treatment, larger amounts of water may be used when it is desired to be able to treat in the form of a paste or a fluid suspension the mineral matter insoluble in water.

Thus, the present invention involves the surprising discovery that mineral materials can be made insoluble in water, which do not respond to the action of silane bonding agents, capable of reacting to the action of these silane bonding agents , by bringing these mineral materials into contact with small amounts of a precipitated metal silicate, insoluble in water and not dried. This discovery is demonstrated by the fact that, when used as fillers or pigments in polymer composites with a silane bonding agent, inorganic water-insoluble and untreated minerals do not produce, in the properties of the final composite product, significant modifications compared to those conferred by the use of the untreated mineral material alone. However, the mineral products which are insoluble in water and which have been treated with a metal silicate according to the present invention very clearly show their response capacity and their activity with regard to the silane binding agents of these polymer composites by conferring better physical properties to the finished composite product. However, the mineral products treated with metal silicate according to the present invention do not produce by themselves, and without silane bonding agent, any significant modification of the properties of the final composite compared to the properties conferred by the untreated mineral matter. Thus, the significant improvements in the properties of the finished composite can only be demonstrated through the use of a combination of the mineral products treated with metal silicate according to the present invention and silane binding agents.

Although one does not wish to be bound by any theory or description of any mechanism, this phenomenon leads to expressing the thought that the mineral products insoluble in water, treated with metal silicate of the present invention , consist essentially of this mineral product having, associated with its surface, a coating of metal silicate insoluble in water. Thus, unlike any sort of form of mixed crystals of mineral fillers or co-precipitated mineral pigments, it is believed that the mineral products treated with metal silicate according to the present invention, and which are prepared from mineral products already formed which are then brought into contact with a water-insoluble metal silicate, are in a laminated or layered form.

As such, the layer or coating of metal silicate on the mineral products treated with metal silicate according to the present invention is not measurable; however, its presence is surely confirmed by the existence of very easily measurable responses of these silicate-treated mineral products to the action of silane binding agents, in terms of properties of the finished polymer composite, as explained above.

Therefore, the metal silicate coatings, associated with the water-insoluble mineral products treated with metal silicate according to the present invention, can completely encapsulate the mineral material used or can only represent a partial coating of a certain portion of the surface of the treated mineral material, or they may consist of an association of distinct fragments of metal silicate at non-contiguous sites of the mineral particles. In addition, these metal silicate coatings can consist of a single compound of metal silicate type or of two or more different compounds of metal silicate type associated with the mineral material treated. When two or more metal silicates are used or are desired, they can be applied in any desired sequence. For example, for a coating consisting of water-insoluble metal silicates A and B, A can be applied first and B applied second, or the reverse order can be used. Furthermore, it is evident that the chemical compositions of the water-insoluble metal silicates used to form the coatings on the water-insoluble and silicate-treated mineral product can vary independently of each other, if we want it. For example, the water-insoluble metal silicate in a given coating may contain one or more metal ions and, for each metal ion, there may be associated a rate or ratio between this metal oxide of SÌO2 (Mx0y / Si02), as explained above, as an independent composition parameter, and these factors can be kept constant or varied according to any predetermined desire by adjusting the starting ratios, the order of addition and the relationships between flow rates or feed rates of the water-soluble metal salt and silicate solutions. In the simplest case involving two metal ions in the silicate coating of the treated mineral material, the average ratio between metal oxides and SiO 2 is used and a coating of metal silicate insoluble in water is obtained. mixed structure. Of course, it is also obvious that one can prepare much more complex coatings within the scope of the present invention, by varying both the structure and the composition of the coating, if desired, as indicated above. above.

As noted above, a third step of the process of the present invention consists in bringing the mineral product treated with a water-insoluble metal silicate, obtained as described above, into contact with an organosilane binding agent chosen from silanes containing functional organic groups and having the formula:

Ra

I

R If (X) 3 — a

(where R, which contains a carbon atom directly linked to the silicon atom of the above formula, represents an organic radical

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comprising at least one functional substituent; R 'represents a radical chosen from R and monovalent hydrocarbon radicals; a is 0 or 1; X represents a hydrolyzable group), the hydrolysates of these silanes, the condensation products of these silanes, and their mixtures.

This modification by an organosilane can be carried out by any technique involving the intimate contact of one or more mineral products, treated with metal silicate insoluble in water, with one or more organosilane binding agents, in isolation or in a mixture, successively or at the same time, as desired. For example, by way of illustration, these organosilane binding agents can be sprayed, in atomized form, in undiluted form or optionally in the form of dispersions or possibly liquid solutions of these organosilane binding agents in water or in inert diluent vehicles, on a mass, subjected to agitation, mineral products treated with silicate insoluble in water, finely divided and which are to be modified. As a variant, liquid suspensions of the mineral products treated with metal silicate insoluble in water can be introduced into a zone of great turbulence, such as in a mixing tee or in the vicinity of a rotary agitator with rapid movement. divided and which are to be modified, as well as the organosilane binding agents in undiluted form or in the form of liquid solutions or dispersions of these binding agents in water or in diluting vehicles. The mineral compositions modified with the organosilane can be recovered by any conventional process and can be used as such or they can be dried at ambient temperatures or at high temperatures, for example at about 100 ° C., by any conventional process that one wishes to apply.

The amount of the organosilane bonding agent which can be used to form the mineral compositions treated with a silicate and modified with a silane according to the present invention is not narrowly fundamental and it can be between approximately 0.01 and 50 parts by weight, and preferably between approximately 0.10 and 10 parts by weight per 100 parts by weight of the mineral product treated with the metal silicate insoluble in water and which must be modified, although, if it is you can use more or less. Similarly, the silane binding agents and the mineral materials to be modified can be brought into contact at any suitable temperature, ambient temperatures being generally preferred, and the operation is carried out, for example, near ambient temperature. The period or duration of contact between the silane bonding agent and the mineral matter to be modified is also not fundamental, and it is only necessary that this period of time suffices to ensure intimate contact between the ingredients in question.

In addition, while the mineral compositions treated with a water-insoluble metal silicate and modified with an organosilane can simply be prepared by bringing an organosilane, in undiluted form, into contact with the mineral product treated with a metal and dried silicate, which is to be modified, it is possible, if desired, as indicated above, to add an inert diluent and / or water to facilitate the handling of the materials in question. Any conventional inert diluent can be used which will not harm the organosilane binding agent or the mineral filler treated with the water-insoluble mineral silicate, nor the resulting mineral composition, treated with silicate and modified by silane. Examples of such inert diluents include hydroxylated compounds, for example alcohols such as methanol, ethanol, propanol, butanol, etc .; hydrocarbons such as hexane, heptane, benzene, toluene, etc .; ethers such as ethyl ether, dipropyl ether, etc. ; esters and ketones, such as ethyl acetate, acetone, methyl ethyl ketone, diethyl ketone, etc. Of course, the amount of water and / or inert diluent that is used or added is not fundamental, since solutions or dispersions of these silanes and / or of these can be used in the present case. mineral products. In fact, the mineral compositions treated with metal silicate and modified with organosilane can be produced by operating in the absence of any addition of water and / or of any addition of an inert diluent.

Of course, it should be understood that the organosilane binding agents which are used for the production of the mineral compositions treated with insoluble metal silicate and modified with the organosilane according to the present invention include and include, in addition to the silanes themselves. the same, the hydrolysis products of these silanes, the condensation products of these silanes and their mixtures. This is entirely obvious to an expert in this field, because the use of water as a diluent can cause hydrolysis and / or condensation of the silane used, due to the presence of the hydrolysable groups on the silane. In fact, if desired, the silane can be hydrolyzed and / or condensed before bringing it into contact with the mineral filler material, treated with silicate and which it is a question of modifying. Such hydrolysis and / or such condensation can or can also be caused by atmospheric humidity conditions and / or by water molecules normally found on the surface of the mineral filler treated with silicate. Of course, it is intended to include in the terms hydrolysis product and condensation product, as they are used here, cohydrolysates and cocondensation products of more than one of these silanes with organic functional groups described above. Thus, while the precise configuration of the structure of the mineral products treated with water-insoluble metal silicate and modified with the organosilane according to the present invention cannot be determined, it must be understood that these products also include and include hydrolysis products, condensation products and mixtures thereof. It should also be understood that the present invention also encompasses mineral products treated with water insoluble metal silicate and modified with organosilane, which is obtained by removal of the inert diluent vehicle if used such a vehicle in the production process.

Organosilane binding agents and / or processes for their preparation are well known in the art, and these agents comprise, for example, silanes comprising functional organic groups and corresponding to the formula:

Ra

I

R- If (X) 3_a

(where R, which contains a carbon atom directly attached to the silicon atom of the above formula, represents an organic radical comprising at least one functional substituent; R 'represents a radical chosen from R and monovalent hydrocarbon radicals containing from 1 to 6 carbon atoms, for example phenyl and alkyl radicals, in particular methyl; a is 0 or 1, preferably 0; X represents a hydrolyzable group), the hydrolysis products of these silanes, the condensation products of these silanes and their mixtures. Examples illustrating the organic radicals having the most preferred functional substituent groups are unsaturated organic radicals such as olefinic radicals, for example vinyl, allyl, γ-methacryloxypropyl, etc .; amino substituted radicals such as aminoalkyl radicals, for example P-aminoethyl, y-amino-propyl, N-P- (aminoethyl) -y-aminopropyl, etc .; epoxy-substituted radicals such as a P- (3,4-epoxycyclohexyl) -ethyl, y-glycidoxypropyl radical, etc .; and mer-capto substituted radicals, such as P-mercaptoethyl, y-mercaptopropyl radicals, etc. Among the most preferred silanic bonding agents, mention may be made of vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris- (2-methoxyethoxy) silane, y-methacryloxypropyltrimethoxysilane, P- (3,4-epoxycyclohexyl ) -ethyltrimethoxysilane, y-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, P-mercaptoethyltriethoxysilane, y-mercaptopropyltrimethoxysilane, P-aminoethyltriethoxysilane, y-aminopropyltriethoxysilane, amino-ethyamino-amino-propane

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Other silanes, which can be used in the practice of the present invention, include the following:

HOOC (CH2) 8CHSi (OCH3) 3 CH3CH2 = CH (CH2) 4CH2Si (OCH3) 3 [■ fCH2CH2ifCH2CH ^]

c = o

I

OH. H2N (CH2) 3Si (OCH2CH3) 3 [-f CH2 CH -f CH2CH -) ■]

J \ Si (OCH3) 3

HOOCCH2CH2Si (OCH2CH3) 3

NCCH2CH2Si (OCH2CH3) 3

H2N (CH2) 4Si (OC2H5) 3

H2NCH2CH2NHCH2CH2NHCH2CH2CH2Si (OC2H5) 3 O

H2N <ü; NHCH2CH2CH2Si (OCH3) 3

CH3

HS - <\ ^ ~ y> ~ CH2CH2Si (° CH2CH3) 3 O O

He 11,

HO CCH = CHC — OCH2CH2CH2Si (OCH3) 3 O

HSCH2CH2CH2 CNH (CH2) 3Si (OCH2CH3) 3 O

HOCH2CH2CH2CH2CH2CNH (CH2) 3Si (OC2H5) 3 (CH3CH20) 3SiCH2CH2CH2S - S - S - CH2CH2CH2Si (OCH2CH3) 3 (CH3CH20) 3Si (CH2) 3 - S - S - (CH2) 3Si (OCH2CH3)

[(CH3CH20) 3SiCH2CH2 CH3] 2 [- S - S - S -]

[(CH30) 3SiCH2CH;

y X

-CH3] 2 [S4]

o o

II

c-nh2

H2N CNHCH2CH2N (CH2) 3Si (OCH3) 3

o h2n-c = o II I

h2nc-nh (ch2) n - (ch2) 2 -nh (ch2) 3Sî (och3) 3

polyethyleneimine - (CH2) 3Si (OCH3) 3 30

polyethyleneimine - [(CH2) 3Si (OCH3) 3] 2

H

O

CH2 — CHSi (OCH3) 3 O

CH3CH2OCNH (CH2) 3Si (OC2H5) 3

O

N (CH2) 3Si (OC2H5) 3

^> - CH2NHCH2CH2N (CH2) 3Si (OCH3) 3 HCl

HOCH2CH2CH2Si (OC2H5) 3

H2NCH2Si (OC2H5) 3 40

HOCH2Si (OCH3) 3

H2NCHCH2Si (OC2H5) 3

CH3

polyazamide [CH2CH2CH2Si (OCH3) 3] i.5 (see "

U.S. Patent No. 3,746,348 for a complete description of silylated polyazamides). CH2 = C (CH3) COO (CH2) 3Si (OCH2CH2OCH3) 3

Ci 50

CH2 = CH <f% CH2NHCH2CH2NHCH2CH2CH2Si (OCH3) s

O

H

CH2 = CH C - NCH2CH2NH (CH2) 3Si (OCH3) 3 O

CH2 = CHCNH (CH2) 3Si (OCH2CH3) 3 CH2 = CHCH2Si (OCH2CH2OCH3) 3 CH2 = C — CH2Si (OCH3) 3

CH3

HSCH2Si (OCH3) 3 HSCH2Si (OCH2CH3) 3

HS — c S-CH2CH2Si (OCH2CH3) 3

ch2

ch2

I

CH2Si (OCH3) 3

etc.

Thus, the present invention involves the additional discovery that it is possible to prepare preformed mineral compositions, treated with metal silicate insoluble in water and modified with organosilanes, and to use these compositions as fillers in polymer / filler composites to give better physical properties (for example a better modulus in action) to the composite finally produced, even in the absence of any additional quantity of ingredients of the organosilane binding agent type in the formulation of the polymer / filler composite. The measurable improvement in the properties of the finished polymer composite, which can be attributed to the use of mineral fillers treated with metal silicate insoluble in water and modified with the organosilane according to the present invention, clearly demonstrates that a clear interaction (that is to say a response or a reaction) occurs between the silane binding agent and the mineral filler treated with the silicate during the production of these charges.

The mineral products treated with metal silicate and the mineral compositions treated with metal silicate and modified with organosilanes, according to the present invention, have a wide range of utility and can serve as reinforcing or reinforcing fillers or pigments in any formulation of known polymer composites generally requiring a filler or pigment, such as rubbers, thermoplastic and thermosetting resins, paints, varnishes, inks, etc., in the same way as mineral fillers classics and mineral pigments have been used so far. In addition, better physical properties are imparted to the finished polymer composite when the mineral compositions treated with metal silicate and modified with organosilane according to the present invention are used, even in the absence of organosilane agents. additional

615,896

8

bonding agent, or else when using the mineral products treated with metal silicate, according to the present invention, as fillers with silanic bonding agents in conventional polymer composites, for example rubbers, resins, etc. Such property improvements can be many and varied depending on the particular materials used. However, such effects are usually easy to determine and are manifested by changes in the values of the characteristic properties of the finished composite, which deviate from the values of the same properties presented in the absence of any silane binding agent. For example, in elastomeric and resinous composites, one often sees the improved effects attributable to the present invention in the finished composite product in terms of its resistance to deformation forces, as they are commonly expressed by the modules in tension, in compression and shear, in increased resistance to abrasion and in decreases in hysteresis losses during bending, and in other such physical properties.

Yet another aspect of the present invention relates to the preparation of polymeric compositions from: a) a polymeric component; b) an organosilane binding agent, and c) as a filler, a mineral product treated with metal silicate; or alternatively: a ') a polymer component, and b') as a filler, a mineral composition treated with metal silicate and modified with an organosilane, and optionally c ') an organosilane binding agent.

It should be understood that compositions of polymer composites can be considered, comprising as essential ingredients the constituents a), b) and c) defined above or, alternatively, a ') and b') and optionally c ' ) as practically equivalent with regard to the development of better properties in the state of the finished composite. However, there may be a preference for assembling particular polymer composites from the aforementioned constituents a), b) and c) rather than from the constituents defined above a ') and b') and optionally c ') , and vice versa, depending on the particular composition of the finished polymer composite that is desired, according to the particular possibilities and the equipment available for assembling the composite, and according to the requirements linked to the end use for which it is intended. the composite. By way of illustration, when it is necessary to use a particular combination of an inorganic product treated with metal silicate c) and an organosilane bonding agent b) in large total quantities at several assembly sites of the polymer composite , it can be very effective and economical to provide the various sites with an equivalent mineral composition, treated with metal silicate and modified with organosilane. Thus, a preference can develop based on factors of efficiency and economy. In addition, a preference may arise from technological factors such as, for example, when a by-product originating from the interaction of an organosilane bonding agent b) and a mineral filler treated with a metal silicate c) is harmful in any way or undesirable; a technological preference may then develop for the other constituent b '), that is to say a charge of equivalent mineral composition, treated with metal silicate and modified with organosilane. Experts in this area will readily consider other examples.

The polymeric constituents of the new composites of the present invention, as well as methods for their preparation, are well known in the art and can include, for example, alone or in addition, any of the homopolymers and synthetic copolymers of monomers olefinics and diolefins such as ethylene, propylene, butylenes, methylpentenes, styrenes, a-methylstyrene, vinyl chloride, vinyl fluoride, vinylidene chloride, acrylonitrile, metacrylonitrile, esters of vinyl alcohol, acrylic acid and its esters and amides, methacrylic acid and its esters and amides, allyl phthalate, butadiene, isoprene, chloroprene, ethylidenenorbornene, 1,5-hexadiene, divinylbenzenes,

etc .; as well as synthetic condensation polymers commonly classified as alkyd resins, polyesters, Nylons, phenolic resins, epoxies, polysulfones, polysulfides, polysulfonates, polysulfonamides, poly-urethanes, polyureas, etc. ., as well as oligomers and polymers from animal and vegetable sources such as cellulose esters and ethers, fatty acid triglycerides of carbon-carbon unsaturation, natural rubber and ficus rubbers, etc. . The preferred polymers are polymers of the rubber type and thermoplastic and thermosetting resins which lead to conventional articles comprising these crosslinked polymers.

Organosilane binding agents, which form part of the new composites of the present invention, as well as the methods for their preparation, are well known in the art, and these agents include the silanes containing functional organic groups defined above, as well as the hydrolysis products and the condensation products of these silanes, and mixtures thereof. The role of a silane bonding agent, of providing a solid chemical bridge between a filler which can react with the silanes and of the polymer which is used, is well known in practice. However, it is of course surprising to note that this role is achieved in polymer / filler composites comprising the constituents a), b) and c) defined above when there is so little silicate used in the form 25 complete lation of the polymer composite. It is also surprising that this can be achieved in polymer / filler composites comprising the constituents a ') and b') defined above, which do not require the presence, in the formulation of the composite, of a any additional amount of organosilane binding agent c '), although such optional ingredient c') can, of course, be used if desired. It should of course be understood that for effective binding action in a particular polymer / filler composite it is necessary to choose the appropriate organosilane binding agent, i.e. an agent which can react suitably with the polymer component and with the filler component in the case of each particular polymer / filler composite that is considered. Thus, there may be more than one silane bonding agent suitable for a particular polymer composite, but a given silane bonding agent may not be suitable for all composites of the polymer. The choice of the most preferred silane bonding agent in the case of any particular polymer composite is well within the domain of routine experimentation.

Of course, the filler forming part of the new compositions of polymer composites of the present invention comprises the mineral products treated with metal silicate (component c) defined above) of the present invention, according to the definition given above. above, and the mineral compositions treated with metal silicate and modified with organosilane (constituent b ′) defined so above), of the present invention, according to the definition given above.

The particular manner of effecting the mixing and finishing of the polymer composite compositions of the present invention, as well as the various amounts of the ingredients that are used, are not fundamental, as this is conventionally known and simply depends the particular finished polymer composite that is to be obtained as well as the end use for which this composite is intended; and conventional operations such as mixing, crosslinking, drying, etc. can be carried out in the same known manner as that used hitherto for conventional polymer composites containing siliceous fillers. In general, the amount of the organosilane bonding agent b) which is used with an inorganic filler treated with metal silicate c) will normally be between approximately 0.1 and 10 parts by weight per 65 100 parts by weight of the mineral filler treated with metal silicate which is used, although higher or lower quantities can be used if this is desirable. Of course, the quantity of the mineral filler treated with metal silicate

9

615,896

[component c)] or the amount of the mineral filler composition treated with metal silicate and modified with organisilane [component b ')] which is used in a given composite can be between such a low value as 0.1 part by weight and a value as high as 300 parts by weight or more, per 100 parts by weight of the polymer that is used, because it simply depends on the desired end product and its use. Of course, the amount of the organosilane bonding agent which is optionally used c ′) can be between a proportion of zero and 10 parts by weight or more per 100 parts by weight of the polymer which is used.

It should be understood that in addition to the essential constituents described above, the new polymer / filler composite compositions of the present invention may also contain, as desired, various other conventional auxiliary ingredients such as softeners, plasticizers and peptization, lubrication agents, conventional particulate and fibrous fillers, dyes and pigments for coloring, antioxidant and anti-zone agents, ultraviolet protection agents, odor modifiers, protection agents against thermal decomposition, crosslinking agents, agents for accelerating the rate of maturation or hardening and activating agents, etc. Of course, the multitude of various conventional applications of finished composite articles is well known to experts in this field.

The following examples are intended to illustrate the present invention and should in no way be taken to limit it. It should be understood that all of the parts, percentages and proportions shown herein are by weight, unless otherwise indicated. The tensile modulus is defined as the tensile stress, in kilograms per square centimeter of original section, necessary to produce a given elongation of a composite sample, and it is usually an elongation of 300% by relative to the length of the sample not subjected to such a constraint.

Example 1

500 parts of wet ground calcium carbonate (calcite ore, Atomite, 2.5 µl; Thomson-Weinman Co.) are added to 2000 parts of water which is stirred rapidly at room temperature (23 ° C) to form a fluid suspension. To this suspension subjected to stirring, 200 parts of a 10% by weight aqueous solution of sodium metasilicate nonahydrate (Na2Si03-9H20) are then added, then added dropwise, over a period of 20 min, 78, 1 parts of an aqueous solution at 10% by weight of anhydrous calcium chloride (CaCl2) in order to provide 1.64 parts of calcium silicate per 100 parts of the calcium carbonate introduced. The mixture is then left to stand until the solids are deposited and the upper aqueous layer is removed by siphoning. The solids are washed twice, each time adding 1000 parts of water, stirring, letting it settle and removing the upper layer by siphoning. To contribute to drying, the solids are then washed by adding 1000 parts of acetone to them, stirring, letting the deposit take place and removing the upper layer by siphoning. The solids are then filtered and dried in an oven at 150 ° C, under a pressure corresponding to 2 mm of mercury, for 4 h. The solids thus dried are pulverized to produce 492 parts of the mineral calcium carbonate, treated with calcium silicate, insoluble in water, which is subjected to an identification analysis indicating that this carbonate contains 1 , 27 parts of calcium silicate (in the form of CaSi03) per 100 parts of the product.

Example 2

The present example illustrates the preparation of a carbonate filler treated with calcium silicate, when a base (NaOH) is used to obtain a calcium silicate having, during its introduction, a Ca0 / SiO2 ratio of 3 / 1.

750 parts of wet ground calcium carbonate (Atomite calcite, 2.5 p .; Thomson-Weiman Co.) are added to 3000 parts of water to form a fluid suspension. To the stirred suspension is added 152.2 parts of a 10% aqueous solution of sodium metasilicate nonahydrate and 85.8 parts of a 10% aqueous solution of sodium hydroxide, then added drop by drop in 20 min 178.5 parts of an aqueous solution at 10% by weight of anhydrous calcium chloride to provide 1.63 part of calcium silicate (having, during its introduction, a Ca0 / Si02 rate or ratio 3/1) per 100 parts of mineral calcium carbonate. The mixture is then left to stand until the solids are deposited and the upper aqueous layer is removed by siphoning. The solices are separated by filtration and washed with water on the filter. The solids thus washed are dried at room temperature for 16 h, then they are dried in an oven for 24 h at 110 ° C.

Example 3

The present example illustrates the preparation of a carbonate filler treated with calcium silicate, during which an acid (HCl) is used to provide a calcium silicate having, when introduced, a Ca0 / SiO2 ratio or level 1/3.

750 parts of wet ground calcium carbonate (Atomite calcite; 2.5 | x; Thomson-Weinman Co.) are added to 3000 parts of water to form a fluid suspension. 441.3 parts of a 10% by weight aqueous solution of sodium metasilicate nonahydrate are added to the suspension, which is stirred, then a mixture of 57.5 parts is added dropwise over 20 minutes. of an aqueous solution at 10% by weight of anhydrous calcium chloride with 75.6 parts of an aqueous solution at 10% by weight of hydrochloric acid to provide 1.63 part of calcium silicate, having, during its introduction, a Ca0 / Si02 ratio or rate of 1/3 per 100 parts of mineral calcium carbonate. The mixture is then worked, washed and dried according to the procedure of Example 2.

Example 4

The present example shows the effect of the treatment of a charge of calcium carbonate with calcium silicate insoluble in water on the action of a silane bonding agent in a rubber compound vulcanized with sulfur.

A series of sulfur vulcanized rubber composites is prepared using the following formulation of the composite in which the nature of the particular mineral filler and the amount of silane used are varied, as indicated in Table 1.

Formulation of the compound Parts by weight

Natural rubber1 50

Styrene / butadiene rubber2 50

Mineral filler 100

Silane binding agent 3 as indicated

Stearic acid 1

Zinc oxide 4

Sulfur 2

NCBS4 1

DPG5 0.3

1 Smoked leaf N ° 1.

2 Butadiene / styrene rubber SBR 1710.

3 3-Mercaptopropyltrimethoxysilane.

* N-Cyclohexylbenzothiazolesulfenamide.

5 Diphenylguanidine.

All the rubber compounds vulcanized with sulfur are prepared by operating in the same way, as follows:

The vulcanizable rubber polymers are introduced into a rubber roller mill with two rollers, cooled by water, a strip is formed there and milled until a smooth and plastic product is obtained. The mineral filler is added to the polymer strip and,

5

10

15

20

25

30

35

40

45

50

55

60

65

615896

10

when used, the silane binding agent is added dropwise at the same time as the mineral filler. After obtaining an intimate mixture of the polymer, the filler and the silane, the vulcanizing agents, the accelerators and other auxiliary ingredients are added, and the mixture is ground until an intimate dispersion is obtained. The mixture is kept at ambient temperature and pressure for at least 16 hours, then it is ground again until a smooth and plastic product is obtained. Pre-formed sheets are cut from the re-ground mixture by molding and vulcanized under a pressure of approximately 70 bars at an elevated temperature of approximately 160 ° C. After a minimum of 16 hours of rest under ambient conditions, measures the physical properties of sulfur vulcanized rubber composites and is noted in Table 1.

In Table 1, charge A represents the use of a wet ground commercial carbonate, untreated, (Atomite calcite, 2.5 | i; Thomson-Weinman Co.). The feed B represents the use of the same mineral filler of calcium carbonate 5 not treated commercially, but after its suspension in water, its washing and its drying as indicated in Example 1 above above. Filler C represents the use of a mineral filler of calcium carbonate treated with water-insoluble calcium silicate, which was prepared using the same ingredients and the same methods as those described in Example 1 above, except that the number of parts by weight of the water-insoluble calcium silicate and precipitated per 100 parts by weight of the calcium carbonate introduced into the aqueous suspension is varied, as indicated in Table 1.

Table 1:

Properties of vulcanized composites

Charge1 Silane2 test

N ° (parts) (parts)

Resistance Module

300% of traction traction (kg / cm2) (kg / cm2)

Elongation at Break Time (Shore A)

(%)

1

AT

None

22.75

91

600

45

2

AT

0.5

22.75

85.75

575

45

3

B

None

24.5

115.5

625

45

4

B

0.5

26.25

127.75

650

45

5

C (0.4)

None

22.75

131.25

650

45

6

C (0.4)

0.5

31.5

140

650

50

7

C (1.6)

None

26.25

138.25

650

50

8

C (1.6)

0.5

49

127.75

650

50

9

C (3.3)

None

21

134.75

650

45

10

C (3.3)

0.5

17.25

136.5

575

50

1 Number of parts of calcium silicate, insoluble in water and precipitated, used to treat 100 parts of calcium carbonate, starting mineral material introduced into the suspension.

2 Number of parts of 3-mercaptopropyltrimethoxysilane used per 100 parts of filler used.

Tests Nos. 1 and 2 show that the untreated calcium carbonate, which is used as mineral filler, does not respond to the action of the silane binding agent. For example, there is no improvement in the result of the traction modulus test. Tests Nos 3 and 4 show that washing by aqueous suspension and drying the untreated calcium carbonate which is used as mineral filler does not influence the response of the charges to the action of the agent binding silane. Tests Nos. 5, 7 and 9 show that, when using calcium carbonate, treated with calcium silicate insoluble in water, as mineral filler used alone, that is to say without silane bonding agent, no effect is observed on the tensile modulus properties of the cured or vulcanized composite article. Tests Nos 6, 8 and 10 illustrate the present invention and they show that the calcium carbonate treated with calcium silicate insoluble in water and which constitutes the mineral filler according to the present invention, of course, responds to the action of the silane bonding agent as shown by significant improvements in the tensile modulus of the cured or vulcanized composite article, when this carbonate treated with silicate is used as mineral filler with the silane bonding agent.

Similar improved results can be obtained, for example by incorporating, in appropriate amounts, calcium carbonate treated with water-insoluble calcium silicate (mineral filler prepared as in Example 1) with a suitable silane agent. bonding in other conventional types of polymer composites, such as thermoplastic resin composites, for example polyethylene, polyvinyl chloride, ethylene / vinyl acetate, etc.

40 Example 5

The present example shows the response of the mineral fillers of the present invention, of the calcium carbonate type treated with calcium silicate insoluble in water, to the action of silane binding agents, in comparison with physical mixtures of silicate fillers of calcium and calcium carbonate.

A series of sulfur-vulcanized rubber composites is prepared, using the same composite formulation and the same procedure as that indicated in Example 4, and using the following formulation:

Composite formulation Parts by weight

Natural rubber1 50

55 Styrene / butadiene rubber2 50

Mineral filler 50

Silanic bonding agent as indicated

Stearic acid 1.5

Zinc oxide 6

60 Sulfur 2

NCBS4 1.1

DPG5 0.7

1 Smoked leaf N ° 1.

65 2 Butadiene rubber / styrene SBR 1710.

3 3-Mercaptopropyltrimethoxysilane.

4 N-Cyclohexylbenzothiazolesulfenamide.

5 Diphenylguanidine.

11

615,896

In this formulation, the nature of the particular mineral filler and the amount of silane that is used are varied as indicated in Table 2.

In Table 2, in tests Nos. 1 to 11, the same composite formulation is used as that indicated in Example 4, while in tests No. 12 to 15, the composite formulation indicated above is used. in this example 5; charge A represents the use of a wet and untreated ground calcium carbonate (Atomite calcite; 2.5 p .; Thomson-Weinman Co.); filler B represents a mixture, operated dry, of filler A and of a precipitated synthetic calcium silicate (Silene EF, Pittsburg Plate Glass Industries); the filler C represents an aqueous suspension of the filler B; Filler D represents the use of a mineral filler of calcium carbonate treated with calcium silicate insoluble in water, which was prepared using the same ingredients and the same process as that described in the example 1, except that 1.57 and 3.1 parts by weight of water-insoluble calcium silicate were precipitated and used for 100 parts by weight of mineral calcium carbonate introduced into the aqueous suspension ; load E represents the use of a mixture, operated dry, of a precipitated synthetic calcium carbonate (Multifex 1DX; 0.05 p .; Diamond-Shamrock Corp.) and of a precipitated synthetic calcium silicate ( Silene EF, Pittsburgh Plate Glass Ind.); and the filler F represents the use of a mineral filler of calcium carbonate treated with water-insoluble calcium silicate, which was prepared using the same ingredients and the same process as that described in the Example 1, except that the calcium carbonate, the starting mineral material that is used, is precipitated synthetic calcium carbonate (Multifex 1DX; 0.05 p; Diamond-Shamrock Corp.), and that is precipitated and uses 1.5 parts by weight of calcium silicate insoluble in water per 100 parts by weight of calcium carbonate introduced into the aqueous suspension. Table 2 also indicates the number of parts by weight of 3-mercaptopropyltrimethoxysilane which is used as a bonding agent per 100 parts by weight of the filler used, as well as the number of parts by weight of calcium silicate which is used. uses per 100 parts by weight of the mineral calcium carbonate used.

Table 2

Silane Module Silicate Charge Test at

N ° calcium (parts in 300% of

(parts by weight) traction by weight) vulcanized composite (kg / cm2)

1

AT

0

0.0

22.75

2

AT

0

0.5

21

3

B

1.25

0.0

24.5

4

B

1.25

0.5

26.25

5

VS

1.25

0.0

24.5

6

VS

1.25

0.5

22.75

7

D

1.57

0.0

26.25

8

D

1.57

0.5

49

9

AT

0

1.5

33.25

10

B

3.0

1.5

40.25

11

D

3.0

1.5

70

12

3

1.5

0.0

35

13

E

1.5

1.5

- 40.25

14

F

1.5

0.0

36.75

15

F

1.5

1.5

71.75

Tests Nos 1 and 2 show that the mineral filler of untreated calcium carbonate which is used does not respond to the action of the silane binding agent and that there is no improvement in the test determining the tensile modulus, even when this load is used with the silane. Tests No 3, 4, 5 and 6 show that physical mixtures of calcium carbonate and calcium silicate, obtained by dry processes (tests Nos 3 and 4) or by wet processes (tests No 5 and 6) are also inert towards the silane binding agent. Tests Nos. 7 and 8 illustrate the present invention and show that the mineral filler of calcium carbonate treated with calcium silicate insoluble in water, according to the present invention, when it is used with the silane binding agent , of course responds to the action of silane, as shown by a significant improvement in the tensile modulus of the hardened or vulcanized composite. A comparison of tests No 9 to 11 again shows that the mineral filler of calcium carbonate treated with calcium silicate insoluble in water according to the present invention (test No 11) can respond to the action of silane and that the improvement in the tensile modulus is not due to the simple presence of calcium silicate. Tests Nos. 12 to 15 also show the same effects for fillers of the present invention (tests Nos 14 and 15) when there is a base of synthetic calcium carbonate having a greater specific contact surface.

Example 6

The present example shows the effect of the time elapsed between the formation of a metal silicate insoluble in water and its contacting with a mineral filler on the possibility of the mineral material, treated with silicate of metal insoluble in l water, to respond to the action of an organosilane binding agent.

A series of sulfur-vulcanized rubber composites is prepared according to the procedure of Example 4, using the following formulation for the composite:

Composite formulation Parts by weight

Natural rubber1 50

Styrene / butadiene rubber2 50

Mineral filler 100

Variable Silane3

Stearic acid 1.5

Zinc oxide 6

Sulfur 2

NCBS4 1.1

DPG5 0.7

1 Smoked leaf N ° 1.

2 Butadiene / styrene rubber SBR 1710.

3 3-Mercaptopropyltrimethoxysilane.

4 N-Cyclohexylbenzothiazolesulfenamide.

5 Diphenylguanidine.

Table 3 shows the properties of sulfur vulcanized rubber articles for cured or vulcanized composites. In this table 3, the charge A represents the use of a charge of calcium carbonate treated with calcium silicate insoluble in water, which is produced using the same ingredients, the same quantities and the same mode. as in Example 1, that is to say that the water-insoluble calcium silicate is precipitated in the presence of the charge of calcium carbonate; the filler B represents the use of a filler treated with calcium silicate insoluble in water and which is produced using the same ingredients, the same quantities and the same procedure as in Example 1, except that the charge of calcium carbonate is brought into contact with the water-insoluble calcium silicate immediately after the precipitation of this silicate has been completed; the load C represents the use of a load of calcium carbonate treated with calcium silicate insoluble in water and which is produced using the same ingredients, the same quantities and the same operating procedure as in Example 1, except that the calcium carbonate charge is not brought into contact with the calcium silicate

5

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25

30

35

40

45

50

55

60

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615,896

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insoluble in water only 10 min after the completion of the precipitation of this silicate; the load D represents the use of a load of calcium carbonate treated with calcium silicate insoluble in water, which is produced using the same ingredients, the same quantities and the same procedure as in Example 1, except that the charge of calcium carbonate is not placed. in contact with calcium silicate insoluble in water for 100 minutes after the precipitation of this silicate has been completed; the load E represents the use of a load of calcium carbonate treated with calcium silicate insoluble in water and which is produced using the same ingredients, the same quantities and the same procedure as at Example 1, except that the charge of calcium carbonate is not brought into contact with the calcium silicate insoluble in water until 1000 min after the precipitation of this silicate has been completed. Table 3 also indicates the quantity of the silane bonding agent which is used, in terms of parts by weight per 100 parts by weight of filler used in each composite (p% c).

Table 3 Properties of the vulcanized composite

Test

Charge

Silane

Module at 300%

Resistance to

Elongation at

Hardness

No.

(p% c)

tensile tensile rupture

(Shore A)

(kg / cm2)

(kg / cm2)

(%)

1

AT

0.0

26.25

103.25

575

59

2

AT

1.5

78.75

110.25

425

62

3

B

0.0

28

117.25

575

59

4

B

1.5

-

61.25

175

64

5

VS

0.0

29.75

119

575

59

6

VS

1.5

-

78.75

250

64

7

D

0.0

28

126

600

60

8

D

1.5

-

68.25

150

64

9

E

0.0

28

115.5

575

60

10

E

1.5

-

85.75

325

64

Example 7

The present example illustrates the response of various mineral fillers treated with water-insoluble metal silicate, according to the present invention, to organosilane binding agents.

Various mineral fillers of calcium carbonate treated with water-insoluble metal silicate are prepared, using the same ingredients and the same procedure as in Example 1, except that the following different water-soluble salts are used : iron (FeCl3), barium (BaCl2), cadmium (CdCl2), cobalt (CoC12-6H20), copper (CuCl2), lead (Pb (02C2H4) 2-3H20), lithium (LiCl), zinc (ZnCl2), beryllium (Be (N03) 2'3H20), magnesium [Mg (NC> 3) 2-6H20], strontium [SrCl2-6H2Ó], manganese (MnCl2 ■ 4H20), nickel (NiCl2 • 6H20), silver (AgN03), mercury (Hg (N03) 2-H20), tin (SnCU-5H20), cerium (Ce (N03) 3-6H20) and zirconium (ZrOCl2 • 8H20), in place of calcium chloride. A series of rubber compounds vulcanized by sulfur is then prepared, according to the procedure of Example 4, using the composite formulation of Example 6 and the various fillers of calcium carbonate treated with a different metal silicate. insoluble in water, prepared above as well as different amounts of the silane binding agent. The particular charge of calcium carbonate treated with water-insoluble metal silicate which is used is indicated by the metal mentioned in table 4, as well as the quantity of metal silicate insoluble in water and precipitated as l 'is used [indicated in parts by weight per 100 parts by weight of the untreated calcium carbonate introduced into the aqueous suspension during the preparation of the calcium carbonate charges treated with the silicate (p% c)]. Table 4 also indicates the quantity of the silane bonding agent which one uses, in parts by weight per 100 parts by weight of the load of calcium carbonate treated with silicate which one uses, as well as the properties articles vulcanized with sulfur (properties of vulcanized composites).

(Table at the top of the next page)

Example 8

This example shows the response of various mineral charges

30 lines treated with metal silicate insoluble in water, of the present invention, to the action of organosilane binding agents.

Various mineral fillers are used, treated with water-insoluble calcium silicate, using the same ingredients and the same procedure as in Example 1, except that barium carbonate (BaCOs) from magnesium carbonate (MgCOs), zinc carbonate (ZnC03), calcium sulfate (CaS04-2H20) and barium sulfate (BaS04) as a mineral filler in place of the mineral calcium carbonate. A series of rubber compounds vulcanized with sulfur is then prepared according to the procedure of Example 4, using the composite formulation of Example 6 and the various different mineral fillers treated with calcium silicate insoluble in water, prepared above, with different amounts of the silane binding agent. The mineral filler treated with water-insoluble calcium silicate 45 which is used in particular is indicated by the mineral material indicated in Table 5, as well as the quantity of water-insoluble calcium silicate precipitate that l 'we use, in terms of. parts by weight per 100 parts by weight of the untreated mineral filler introduced into the aqueous suspension during the preparation of the mineral fillers treated with calcium silicate (p% c). By way of comparison, hardened or vulcanized composites are also produced by operating in the same way and using untreated mineral fillers. Table 5 also indicates the amount of the silane bonding agent that is used, in terms of 55 parts by weight per 100 parts by weight of the filler used in the composite (p% c), and the properties of the articles. made of sulfur vulcanized rubber (properties of vulcanized composites).

(Table on next page)

60

Example 9

The present example illustrates the effect of the variation in the rate or the ratio of metal oxide on the response capacity of the mineral fillers treated with water-insoluble metal silicate according to the present invention with regard to the agents. organosilane binding.

Four mineral fillers of calcium carbonate treated with water-insoluble calcium silicate are prepared and used

13

615,896

Table 4: Properties of the hardened composite

Metal Silicate Test Processing Module Elongation Resistance to

No. of metal at 300% (kg / cm2) tensile (kg / cm2) failure (%)

(p% c)

<Silane (p% c) ►

0 1.5 0 1.5 0 1.5

1

None

None

29.75

36.75

119

89.25

575

450

2

Iron

1.85

54.25

70

92.75

80.5

400

375

3

Barium

3.0

28

63

127.75

133

600

550

4

Cadmium

2.65

35

77

136.5

129.5

575

475

5

Cobalt

1.9

28

61.25

134.75

145.25

600

575

6

Copper

1.96

29.75

47.25

138.25

141.75

650

575

7

Lead

3.98

26.25

35

127.75

133

600

675

8

Lithium

1.26

29.75

54.25

133

126

600

550

9

Zinc

1.99

24.5

77

133

141.75

625

500

10

Beryllium

1.0

28

-

136.5

64.75

625

250

11

Magnesium

1.0

28

-

115.5

64.75

600

200

12

Strontium

1.0

28

57.75

127.75

87.5

600

375

13

Manganese

1.0

28

-.

124.25

70

625

225

14

Nickel

1.0

28

59.5

119

98

575

450

15

Silver

1.0

29.75

43.75

112

94.5

550

500

16

Mercury

1.0

28

49

122.5

98

600

475

17

Tin

1.0

28

54.25

108.5

101.5

575

450

18

Cerium

1.0

24.5

-

101.5

63

575

300

19

Tirconium

1.0

24.75

54.25

129.5

101.5

575

425

Table 5:

Properties of the vulcanized composite

Test

Material

Silicate

Silane

Module

Resistance to

Elongation at

No.

Ca mineral

(p% c)

traction at

tensile breaking

(p% c)

300% (kg / cm2)

(kg / cm2)

(%)

1

BaC03

None

0.0

22.75

147

600

2

BaCC> 3

None

1.5

59.5

64.75

325

3

BaCC> 3

1.6

0.0

22.75

154

600

4

BaCC> 3

1.6

1.5

64.75

155.75

525

5

MgCOs

None

0.0

59.5

103.25

450

6

MgC03

None

1.5

73.5

120.75

450

7

MgCOa

1.6

0.0

57.75

99.75

450

8

MgCOs

1.6

1.5

129.5

131.25

300

9

ZnC03

None

0.0

38.5

89.25

450

10

ZnCC> 3

None

1.5

52.5

108.5

475

11

ZnC03

1.6

0.0

43.75

94.5

450

12

ZnCC> 3

1.6

1.5

66.5

94.5

375

13

CaS04-2H20

None

0.0

17.5

38.5

475

14

CaS04-2H20

None

1.5

38.5

54.25

425

15

CaS04-2H20

1.6

0.0

35

108.5

550

16

CaS04-3H20

1.6

1.5

52.5

115.5

475

17

BaS04

None

0.0

22.75

112

550

18

BaS04

None

1.5

-

50.75

250

19

BaS04

1.6

0.0

21

124.25

600

20

BaS04

1.6

1.5

52.5

134.75

525

to produce sulfur vulcanized rubber composites according to the procedure of Example 4, using the composite formulation of Example 6. The properties of the vulcanized composite are indicated in Table 6. The charge A represents the use of untreated calcium carbonate (Atomite; 2.5 n; Thomson-Weinman Co.); Filler B represents the use of a mineral filler of calcium carbonate treated with calcium silicate insoluble in water, prepared using the same ingredients and the same procedure as in Example 3; filler C represents the use of a mineral filler of calcium carbonate treated with calcium silicate insoluble in water, prepared using the same ingredients and the same procedure as in Example 1;

615,896

14

the load D represents the use of a mineral load of calcium carbonate treated with calcium silicate insoluble in water, prepared using the ingredients and the procedure indicated in example 2. The amount of calcium silicate insoluble in water, precipitated and used in the preparation of each of these carbonate charges treated with silicate, is. 1.6 parts by weight of calcium carbonate introduced into the preparation of these fillers treated with silicate. Each composite formulation that is used also contains 1.5 parts by weight of silane per 100 parts by weight of the mineral filler used in the composite. Table 6 also indicates, for each filler used in a composite, the rate or ratio of metal oxide (Ca0 / Si02).

Table 6 Properties of the vulcanized composite

Test

Charge

Ca0 / Si02

Module

Resistance

Elongate

No.

of

to the lie to the

traction at

tensile failure

300%

(kg / cm2)

(%)

(kg / cm2)

1

AT

0

38.5

66.5

450

2

B

0.3

77

87.5

350

3

B

0.5

79

105

450

4

VS

1.0

66.5

98

450

5

D

2.0

56

94.5

475

6

D

3.0

56

92.75

450

Example 10

The present example illustrates the effect of mineral fillers treated with metal silicate insoluble in water, prepared by the consecutive use of two silicates of different metals insoluble in water.

A series of mineral fillers of calcium carbonate treated with metal silicate insoluble in water is prepared, using the same ingredients and the same procedure as in Example 1, except that, in each case, two solutions of water-soluble salts of different metals to the aqueous suspension of calcium carbonate and to the sodium metasilicate solution, successively and in the order indicated below. The compounds to be reacted in calculated amounts are used to provide equal volumes of each precipitated metal silicate, i.e. 0.25 ml of the precipitated metal silicate per 100 parts by weight of the calcium carbonate introduced. Then, sulfur-vulcanized rubber composites are prepared using these inorganic fillers of calcium carbonate treated with water-soluble metal silicate, by the same procedure as that indicated in Example 4, using the same formulation. of composite than that indicated in Example 6 above. When used, the amount of 3-mercaptopropyltrimethoxysilane (binding agent) is 1.5 parts by weight per 100 parts by weight of the filler used in the composite. Table 7 indicates the mineral charges of calcium carbonate treated with water-insoluble metal silicate which is used in each particular case, as well as the properties of the vulcanized composite (case of articles of rubber vulcanized with sulfur). In Table 7, the charge A represents the use of a mineral charge of calcium carbonate treated with barium silicate and with calcium silicate, prepared in the manner described above by the successive use of solutions of calcium chloride and barium chloride, water-soluble salts, in order to precipitate, in the order indicated, calcium silicate and barium silicate which are salts insoluble in water; the filler B represents the use of an inorganic filler of calcium carbonate treated with calcium silicate and with barium silicate insoluble in water, which is prepared in the manner described above using successively solutions of barium chloride and sodium chloride (water-soluble salts) in order to precipitate, in the order indicated, the barium and calcium salts insoluble in water; the filler C represents the use of a mineral filler of calcium carbonate treated with zinc silicate and with calcium silicate insoluble in water, this filler being prepared in the manner described above by the consecutive use solutions of calcium chloride and zinc chloride (water-soluble salts) in order to precipitate, in the order indicated, calcium silicate and zinc silicate which are salts insoluble in water; the filler D represents the use of an inorganic filler of calcium carbonate treated with calcium silicate and with zinc silicate insoluble in water, this filler having been prepared in the manner described above by the use consecutive solutions of zinc chloride and calcium chloride (water-soluble salts) in order to precipitate, in the order indicated, zinc silicate and calcium silicate insoluble in water; the filler E represents the use of a mineral filler of calcium carbonate treated with zinc silicate and with barium silicate insoluble in water, which is prepared in the manner described above using solutions of barium chloride and zinc chloride (water-soluble salts) in order to precipitate, in the order indicated, barium silicate and zinc silicate (water-insoluble salts); and the filler F represents the use of a mineral filler of calcium carbonate treated with barium silicate and with zinc silicate insoluble in water, which is prepared in the manner described above using consecutive solutions of zinc chloride and barium chloride (water-soluble salts) in order to precipitate, in the order indicated, zinc silicate and barium silicate (water-insoluble salts).

Table 7 •

Test

Charge

Silane

Module

Resis

Elongate

No.

(p% c)

from tance to

lying to the

traction at

tensile breaking

300%

(kg / cm2)

(%)

(kg / cm2)

1

AT

0.0

28

131.25

575

2

AT

1.5

33.25

112

525

3

B

0.0

29.75

105

525

4

B

1.5

57.75

131.25

500

5

VS

0.0

29.75

117.25

575

6

VS

1.5

82.25

127.75

450

7

D

0.0

26.25

131.75

600

8

D

1.5

75.25

115.5

425

9

E

0.0

28

124.25

575

10

E

1.5

84

113.75

400

11

F

0.0

25.5

124.25

600

12

F

1.5

89.25

108.5

350

Example 11

The present example illustrates the effect of mineral fillers treated with metal silicate insoluble in water, prepared by the consecutive use of two silicates of different metals insoluble in water.

A series of mineral fillers of calcium carbonate treated with metal silicate insoluble in water is prepared, using the same ingredients and the same procedure as in Example 1 above, except that in each case , two solutions of different water-soluble metal salts are mixed before adding them to the aqueous suspension of calcium carbonate and to the sodium metasilicate solution. The compounds to be reacted are used in calculated amounts to provide equal volumes of the precipitated water-insoluble metal silicate, i.e., 0.5 ml of water-insoluble metal silicate coprecipitated.

5

10

15

20

25

30

35

40

45

50

55

60

65

15

615,896

100 parts by weight of the calcium carbonate introduced as a filler. Then, sulfur-vulcanized rubber composites are prepared using these mineral fillers of calcium carbonate treated with mixed metal silicate, insoluble in water, thus prepared, by the same procedure as in Example 4, however as the same composite formulation is used as in Example 6. The amount of 3-mercaptopropyltrimethoxysilane, when used, is 1.5 parts by weight of the filler used in the composite. Table 8 indicates the specific loads of calcium carbonate treated with mixed silicates of water-insoluble metals which are used, as well as the properties of the vulcanized composite (in the case of articles of rubber vulcanized with sulfur). In Table 8, the charge A represents the use of a mineral charge of calcium carbonate treated with a mixture, insoluble in water, of calcium silicate and barium silicate, prepared as described above. using a premixed solution of water-soluble calcium chloride and barium chloride to co-precipitate the mixture of water-insoluble calcium and barium silicates; the filler B represents the use of an inorganic filler of calcium carbonate treated with a mixture of calcium silicate and zinc silicate (insoluble in water), which is prepared in the manner described above in using a solution which is a premix of calcium chloride and zinc chloride (water-soluble salts) so as to co-precipitate the mixture of calcium silicate and zinc silicate (water-insoluble salts); Filler C represents the use of a mineral filler of calcium carbonate treated with a mixture of barium silicate and zinc silicate (water-insoluble silicates), filler prepared as described above using a solution which is a premix of barium chloride and zinc chloride solutions (water-soluble salts) so as to co-precipitate the mixture of barium silicate and zinc silicate (water-insoluble salts).

Table 8

Test

Charge

Silane

Module

Resis

Elongate

No.

(p% c)

at 300%

tance to

lying to the

allon the tensile break

gement

(kg / cm2)

(%)

(kg / cm2)

1

AT

0.0

21

105

600

2

AT

1.5

103.25

105

300

3

B

0.0

26.25

110.25

575

4

B

1.5

78.75

113.75

400

5

VS

0.0

26.25

115.5

575

6

VS

1.5

71.75

129.5

475

Note: p% c = parts by weight per 100 parts of filler.

Example 12

The present example illustrates the response capacity of mineral fillers, treated with silicates of different metals insoluble in water, to different organosilane binding agents in different formulations of composites.

Various mineral fillers of calcium carbonate treated with silicates of water-insoluble metals are used, using the same ingredients and the same procedure as in Example 1, except that different metal salts are used. water-soluble. The mineral filler of calcium carbonate treated with a particular metal silicate insoluble in water which is prepared and used in the present example is indicated by the metal cited in Tables 9, 10 and 11 which also cite the amount of silicate. of metal insoluble in precipitated water and used (in terms of parts by weight per 100 parts by weight, p% c) of the untreated calcium carbonate introduced into the aqueous suspension during the preparation of the charge of treated calcium carbonate by silicate. For example, in Tables 9, 10 and 11, the load A represents the use of a load of untreated calcium carbonate (Atomite; 2.5 n, Thomson-Weinman) as a comparison control, while the filler B represents the use of a filler of calcium carbonate treated with calcium silicate insoluble in water, which is prepared in the manner described above using calcium chloride, water-soluble salt, this filler having a metal oxide (Ca0 / Si02) ratio or level of 1/3; charge C represents the use of a charge of calcium carbonate treated with barium silicate insoluble in water, which is prepared in the manner described above, using barium chloride (water-soluble salt) , this charge having a rate or ratio of metal oxide (Ba0 / Si02) of 1/1; the filler D represents a filler of calcium carbonate treated with zinc silicate insoluble in water, which is prepared in the manner described above using a zinc chloride (water-soluble salt), this filler having a content or metal oxide (Zn0 / Si02) ratio of 1/1; the charge E represents a charge of calcium carbonate treated with calcium silicate insoluble in water, which is prepared in the manner described above using calcium chloride (water-soluble salt), this charge having a ratio or metal oxide (Ca0 / Si02) level of 1/1.

The calcium carbonate fillers treated with water insoluble metal silicate are then used in various composite formulations. Tables 9, 10 and 11 indicate the properties of the vulcanized composites, in the case of the vulcanized articles thus prepared. All the vulcanized composite articles are prepared by operating in the same way, following the procedure of Example 4, except that different formulations of vulcanizable composites are used. For example, for Table 9, the following formulation of vulcanizable composites was used:

Composite formulation Parts by weight

EPDM1 100 rubber

Mineral filler2,100

Silane binding agent 3 as indicated

Ethylene glycol dimethacrylate 4

Dicumyl peroxide, recrystallized 1.6

1 Royalene 501 (Uniroyal Corp.), ethylene rubber, propylene rubber and a monomeric diene.

2 Varies as shown.

3 Varies as shown.

In Table 10, the following vulcanizable composite formulation was used:

Composite formulation Parts by weight

Chloroprene rubber1 100

Mineral filler2,100

Silane binding agent3 as shown

0.5 stearic acid

Zinc oxide 5

Magnesium oxide 4

Softening oil4 7.5

TMTU5 0.5

1 Neoprene W (DuPont Co.).

2 Variable, as shown.

3 Variable, as shown.

4 Circosol 4240.

5 Tetramethylthio-urea.

In Table 11, the following formulation of vulcanizable composites was used:

5

10

15

20

25

30

35

40

45

50

55

60

65

615,896

16

Composite formulation Parts by weight

Nitrile rubber1 100

Mineral filler2,100

Silane binding agent3 as indicated

Stearic acid "1.5

Zinc oxide 5

Sulfur 1.75

Mercaptobenzothiazyl disulfide 1.5

Tetramethylthiuram disulfide 0.5

Dibutyl phthalate 20

1 Hycar 1052 (B.F. Goodrich Chem. Co.).

2 Variable, as shown.

3 Variable, as shown.

When used, the amount of the silane bonding agent is butadiene-1,3) as the bonding agent; silane C represents the utility

expressed in Tables 9, 10 and 11 in terms of parts by weight for the use of a methacryloxypropyltrimethoxysilane as agent 100 parts by weight of the mineral filler used in the bonding composite. In Table 10, silane D represents the use of a

(p% c). In Table 9, silane A represents the use of a vinyl-3-aminopropyltrimethoxysilane as a binding agent. To triethoxysilane as a binding agent; silane B represents the tables 10 and 11, silane E represents the use of a 3-mercapto-

lization of an isoprenyltrimethoxysilane (l-trimethoxysilyl-3-methylpropyltrimethoxysilane as a binding agent.

Table 9:

Properties of EPDM rubber vulcanized with a peroxide

Test No

Charge

Metal

Silicate

(p% c)

Type

Silane

(p% c)

Traction module at 300%

(kg / cm2)

1

AT

None

0.0

None

0.0

21

2

B

It

1.6

None

0.0

22.75

3

VS

Ba

3.0

None

0.0

21

4

D

Zn

2.0

None

0.0

22.75

5

AT

None

0.0

AT

1.0

24.5

6

B

It

1.6

AT

1.0

36.5

7

VS

Ba

3.0

AT

1.0

35

8

D

Zn

2.0

AT

1.0

35

9

AT

None

0.0

B

1.0

31.5

10

B

It

1.6

B

1.0

_ *

11

VS

Ba

3.0

B

1.0

57.75

12

D

Zn

2.0

B

1.0

75.25

13

AT

None

0.0

VS

1.0

29.75

14

B

It

1.6

VS

1.0

68.25

15

VS

Ba

3.0

VS

1.0

52.5

16

D

Zn

2.0

VS

1.0

84

* Not determinable, since an excessive response at the level of 1.0 part of silane per 100 parts of filler produces a composite elongation of less than 300%.

Table 10:

Properties of chloroprene rubber vulcanized using a metal oxide

Test

Charge

Silicate

Silane

Module

Resistance to

No.

Metal

(p% c)

Type

(p% c)

traction at 300%

tear

(kg / cm2)

(kg / cm2)

1

AT

None

0.0

None

0.0

26.25

11.2

2

E

It

.1.6

None

0.0

26.25

11.9

3

AT

None

0.0

D

1.0

24.5

10.5

4

E

It

1.6

D

1.0

61.25

15.4

5

AT

None

0.0

E

1.0

40.25

12.6

6

E

It

1.6

E

1.0

87.5

12.6

17

Table 11:

Properties of sulfur vulcanized butadiene / acrylonitrile rubber

615,896

Load test Silicate Silane Module at 300% Resistance to

Metal No. (p% c) Type (p% c) of tear pull

(kg / cm2) (kg / cm2)

1 A None 0.0 None 0.0 12.25 3.5

2 D Ca 1.6 None 0.0 12.25 4.2

3 C Zn 2.0 None 0.0 12.25 4.2

4 A None 0.0 E 1.5 12.25 3.5

5 D Ca 1.6 E 1.5 21 6.3

6 C Zn 2.0 E 1.5 24.5 7

Example 13

1.29 kg of sodium metasilicate nonahydrate (Na2Si03 -9H20) and 18.91 of water are added to a 113.51 container fitted with a mechanical stirrer.

dissolution of the sodium salt. Then added 37.81 of an aqueous suspension at 50% by weight of wet ground calcium carbonate (26.3 kg of CaCO 3, calcite of Atomite brand of 2.5 (i, Thomson-Weinman Co.) and the the mixture is stirred for approximately 10 minutes and then 5.03 kg of a 10% by weight aqueous solution of anhydrous calcium chloride (CaCl 2) are added in small 500 ml portions every 5 minutes. all of the CaCl2, the mixture is stirred for 2 hours, then the mineral product of calcium carbonate treated with calcium silicate insoluble in water is filtered, as is desired by its separation from the reaction mixture, and this mineral product is dried.

Example 14

A series of sulfur vulcanized rubber composites are prepared using the following composite formulation in which the particulate mineral filler used is the calcium carbonate mineral product treated with water insoluble calcium silicate of example 13 and in which the quantity of silane which is used is varied, as indicated in table 12.

Formulation of the composite Quantity (g)

Natural rubber1 100

2,100 styrene / butadiene rubber

Mineral filler 3,200

Silanic bonding agent4 as indicated

Stearic acid 3

Zinc oxide 12

Sulfur 4

N-cyclohexyl-2-benzothiazolesulfenamide .. 2.2

Diphenylguanidine 1,4

1 Smoked leaf N ° 1.

2 SBR 1710 rubber.

3 Calcium carbonate mineral product treated with calcium silicate insoluble in water of Example 13.

4 3-Mercaptopropyltrimethoxysilane.

All the rubber compounds vulcanized with sulfur are prepared by operating in the same way, following the procedure indicated in Example 4 and vulcanized on a press at approximately 160 ° C. The physical properties of the sulfur vulcanized rubber composites are measured, and these properties are presented in Table 12.

Table 12:

Properties of vulcanized composites

Silane test Traction module Elongation resistance Shore A hardness

No. (ml) at 300% tensile strength at break '

(kg / cm2) (kg / cm2) (%)

1 None 27.3 21,525 55

2 1.0 49 94.5 475 55

3 2.0 65.5 110.8 425 56

4 3.0 69.3 109.9 425 56

Tests Nos 2 to 4 show that, when the mineral filler of calcium carbonate treated with calcium silicate according to the present invention is used with the silane binding agent, this mineral filler responds well to the action of silane , as indicated by the significant improvement in the tensile modulus of the vulcanized composite.

Example 15

The present example shows the production of a mineral filler of calcium carbonate treated with calcium silicate insoluble in water and modified with organosilane.

Approximately 2724 g of calcium carbonate treated with water-insoluble calcium silicate, product of Example 13, is thoroughly mixed with approximately 27.24 g of γ-methacryloxypropyl-trimethoxysilane in the presence of approximately 120 ml a diluent consisting of aqueous alcohol (90% methanol and 10% water) in a twin barrel mixer at room temperature for

60 about 10 to 15 mins. The mineral filler treated with silicate and modified with silane, the desired product thus formed, is then recovered, and this product is dried for 1 hour at approximately 110 ° C.

Example 16

65 A series of crosslinked polyethylene composites is prepared, using the following formulation of the composite in which the particular mineral filler and the amount of silane used are varied.

615,896

18

Composite formulation Parts by weight

Polyethylene resin 100

Mineral filler 120

Silanic bonding agent1 as indicated

Blue pigment2 1.5

Antioxidant3 1.1

Crosslinking agent4 3.9

1 Y-methacryloxypropTyltrimethoxysilane.

2 Blue pigment F-6279 (Ferro Corp.).

3 Age Rite Resin D; it is a polymerized 1,2-dihydro-2,2,4-trimethylquinoline (R.T. Vanderbilt Co.).

4 Dicup 40 KE; dicumyl peroxide (Hercules Inc.). 15

All the crosslinked polyethylene composites are prepared by operating in the same way as follows:

The polyethylene resin is introduced into a two roller mill (grinding temperature: front roller 76.7 ° C; rear roller 82.2 ° C; 4.55 bar pressure) and a strip is formed as the it is ground until a smooth, plastic product is obtained. Half of the mineral filler is added to the polymer strip and, when used, the silane bonding agent is added dropwise, together with the mineral filler, and kneaded thoroughly . The rest of the charge is then added and kneaded thoroughly, then the other ingredients (antioxidant,

peroxide and pigment) which is also kneaded thoroughly. The composite formulation is then removed from the rollers and molded by crosslinking or vulcanizing the composite formulation for 20 min in a mold under compression at 160 ° C. The average physical properties of the crosslinked polyethylene composites are measured. These properties are shown in Table 13.

In Table 13, the load A of test No. 1 represents the use of a commercial calcium carbonate, ground, wet and untreated (calcite brand Atomite; 2.5 n; Thomson-Weinman Co.) ; no silane binding agent is used in the composite formulation of this test No. 1. Load B of test No. 2 represents the use of the mineral product of calcium carbonate treated with calcium silicate insoluble in water (product of Example 13), but no silane binding agent is used in the formulation of the composite of this test No. 2. The charge C of test No. 3 shows the use of the mineral composition of calcium carbonate treated with calcium silicate insoluble in water, modified with organosilane (product of Example 15), and no other is used silane binding agent in the formulation of the composite of this test No. 3. The load D of test No. 4 represents the use of the mineral product of calcium carbonate treated with calcium silicate insoluble in water (product of Example 13), and the formulation of the composite of this test No. 4 also contains 1.2 parts by weight (per 100 parts by weight polyethylene used) of Y-methacryloxypropyltrimethoxysilane. In tests Nos 1 and 2 of table 13, the mean tensile modulus was measured at 300% whereas, for tests Nos 3 and 4, this measurement was carried out at 200%.

20

25

Table 13:

Properties of vulcanized composites

Load test Tensile strength Elongation resistance Shore A hardness

Mineral number (kg / cm2) tensile strength at break

(kg / cm2) (%)

1 A 80.5 138.2 500 95

2 B 85.05 106.3 440 96

3 C 138.3 140 250 95

4 D 131.4 131.4 250 95

The comparison of tests Nos 1 and 2 shows that poor results are obtained in the measurement of the tensile modulus in the case of crosslinked composites when the mineral filler of untreated calcium carbonate is used or the mineral filler of calcium carbonate treated with calcium silicate, but without silane binding agent. Tests Nos. 3 and 4, which highlight the present invention, show that greatly improved results are obtained for the tensile modulus of the crosslinked composites when using the mineral filler of calcium carbonate treated with silane-modified calcium silicate, even without any additional addition of silane binding agent, and when using the calcium carbonate mineral filler treated with calcium silicate with a silane binding agent. Thus, tests Nos 3 and 4 show that the mineral filler of calcium carbonate treated with calcium silicate can respond to the action of the silane bonding agent as well when this charge is modified by the silane bonding agent before the addition of this filler to the formulation of the composite than when this filler is used separately with the silane binding agent in the formulation of the composite.

Example 17

The present example shows the production of a mineral filler of calcium carbonate treated with calcium silicate insoluble in water and modified with organosilane.

Approximately 2.27 kg of the mineral product '45 of calcium carbonate treated with calcium silicate insoluble in water (product of Example 13) is mixed with approximately 22.7 g of vinyl-tris- ( 2-methoxyethoxy) silane in the presence of approximately 120 ml of a diluent formed by aqueous alcohol (90% methanol and 10% water) in a twin barrel mixer at ambient temperature for approximately 10 to 15 mins. The mineral filler treated with silicate and modified with silane is then recovered, constituting the desired product thus formed, and this product is dried in an oven for 2 hours at approximately 107 ° C. It is found that by using this inorganic filler of calcium carbonate treated with calcium silicate 55 insoluble in water and modified with silane, the properties of tensile modulus of an elastomer composite vulcanized by sulfur are improved, by compared to the same composite in which an untreated calcium carbonate mineral filler is used. This shows the action of the silane bonding agent and the ability of the mineral filler of calcium carbonate treated with calcium silicate to respond to this action of the silane bonding agent during the production of the filler. mineral treated with silicate and modified with silane.

65 Example 18

The present example shows the production of a mineral filler of calcium carbonate treated with calcium silicate insoluble in water and modified with organosilane.

19

615,896

About 2.27 kg of the calcium carbonate mineral product treated with calcium silicate insoluble in water (product of Example 13) are mixed in a thorough manner with about 22.7 g of y-metha-cryloxypropyltrimethoxysilane in the presence approximately 120 ml of a diluent consisting of aqueous alcohol (90% methanol and 10% s of water) in a twin barrel mixer at room temperature for approximately 10 to 15 minutes. The mineral filler treated with the silicate and modified with the silane is then recovered, constituting the desired product thus formed, and this product is dried in an oven for 2 hours at approximately 107 ° C. It is found that by using the inorganic filler of calcium carbonate treated with calcium silicate insoluble in water and modified with silane, the properties of tensile modulus of an elastomer composite vulcanized by sulfur are improved, by with respect to the properties of the same composite in which a mineral filler of untreated calcium carbonate was used. This shows the responsiveness of the mineral filler of calcium carbonate treated with calcium silicate and the silane binding agent for the production of the mineral filler treated with silicate and modified with silane.

20

Example 19

The present example shows the production of a mineral filler of calcium carbonate treated with calcium silicate insoluble in water and modified with organosilane.

About 2.27 kg of the mineral calcium carbonate product treated with calcium silicate insoluble in water (product of Example 13) are mixed in a thorough manner with about 22.7 g of γ-amino-propyltriethoxysilane in the presence approximately 120 ml of a diluent consisting of aqueous alcohol (90% methanol and 10% water) in a twin barrel mixer at room temperature for approximately 10 to 15 minutes. The mineral filler treated with silicate and modified with silane is then recovered, constituting the desired product thus formed, and this product is dried in an oven for 2 h at approximately 107 ° C. It is found that by using this mineral filler of calcium carbonate treated with calcium silicate and modified with silane, the properties of the tensile modulus of a thermoplastic polyvinyl chloride composite are improved compared to the properties of the same composite in which used an untreated calcium carbonate mineral filler. This shows the ability of the mineral filler of calcium carbonate treated with calcium silicate and the silane binding agent to respond to the production of the mineral filler treated with silicate and modified with silane.

r

Claims (9)

615,896 1. A process for preparing a silicate mineral product modified with an organosilane, characterized in that: a) the surface of a mineral matter insoluble in water is put in the presence of water and which is chosen from metal carbonates, metal sulfates and their mixtures, the metal being chosen from barium, calcium, magnesium, zinc, strontium, beryllium and their mixtures, in contact with a metal silicate insoluble in water , precipitated and not dried, the metal of this silicate being chosen from aluminum, barium, berylium, cadmium, calcium, cobalt, copper, iron, lead, lithium, magnesium, manganese , mercury, nickel, silver, strontium, tin, zinc, zirconium and rare earth metals having atomic numbers between 57 and 71, inclusive, and their mixtures, the amount of silicate used between 0.1 part by weight and 20 parts by weight per 100 parts by weight of the material mineral used; b) drying the silicate on the surface of the mineral material; c) the product is brought into contact with an organosilane binding agent chosen from silanes with a functional organic group corresponding to the formula: Ra R-Si— (X) 3_a where R, which contains a carbon atom directly linked to the silicon atom of the above formula, represents an organic radical comprising at least one functional group as a substituent; R 'represents a radical chosen from R and a monovalent hydrocarbon radical; a is 0 or 1, and X represents a hydrolyzable group, or with a hydrolysis product of these silanes, a condensation product of these silanes or their mixtures. 2. Method according to claim 1, characterized in that the mineral material is calcium carbonate. 2 3. Method according to claim 2, characterized in that the calcium carbonate is of natural origin. 4. Method according to claim 2, characterized in that the metal of the silicate is chosen from barium, calcium and zinc. 5. Method according to claim 4, characterized in that the silicate is a calcium silicate. 6. Method according to claim 4, characterized in that, in silicate, the ratio between the metal oxide and SiO2 is less than 3.1 and the amount of silicate used is between 0.3 and 10 parts by weight per 100 parts by weight of the calcium carbonate used. 7. Method according to claim 1, characterized in that, during stage a), the silicate is precipitated in the presence of the mineral matter. 8. Method according to claim 6, characterized in that, during stage a), the silicate is precipitated in the presence of calcium carbonate. 9. Application of the method according to claim 1 to the preparation of a polymer containing the silicate mineral product and modified with an organosilane as filler, characterized in that the modified mineral product is first prepared and added to a polymer or in that step c) of the process according to claim 1 is carried out in the presence of a polymer.