DE2546061A1 - SILICA-COATED SILICA MINERALS AND THE PROCESS FOR THEIR PRODUCTION - Google Patents

Description

An organosilane can be one of the following two classes of material choose: organosilanes, which give the mineral an oleophilic surface; or organosilanes, which are the mineral surface Enabling additional chemical bonds with reactive sites within certain polymers and prepolymers to build. The mineral products of this invention which have been treated to obtain oleophilic surfaces represent are and are superior rheology control additives in lubricants, polyolefins, paints, and oil well fluids also heat and moisture resistant reinforcing agents for rubbers; while those mineral products that are under receipt of surfaces which can chemically react with polymers and prepolymers incorporated into such Systems that give the final composite materials improved mechanical properties as well as heat and moisture resistance.

The invention relates to the field of phyllosilicate minerals such as serpentines and mica and certain fibrous amphiboles, such as amosite, orcidolite, attapulgite and actinolite, which in their structure successively octahedral layers, the oxides of magnesium, aluminum and / or iron contain, and have tetrahedral layers of silicon and oxygen; these minerals have been modified with the Aims to make them oleophilic or to give them certain other desirable properties by using organosilanes were coated. The invention also relates to a method for conditioning these minerals in order to carry out a reaction to enable their surfaces with organosilanes, as well as processes for the production of coatings on these minerals with organosilanes.

It is known that certain phyllosilicates and fibrous amphibole minerals have good properties for use in plastics and in elastomer compounding. In such applications the most important active functions of these materials are reinforcement, the improvement of mechanical properties

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properties, heat resistance and flow control. Besides the above Certain of these minerals have uses as additives in river systems oil-based, such as lubricants, paints and oil well fluids to modify flow properties Application found. In such applications, unmodified minerals are limited in that they are preferred are wetted by water instead of oil, so that composite materials incorporating them generally deteriorated one Develop their effect in the presence of moisture. In addition, the unmodified minerals usually do not come with it Oils, plastics and elastomers interact positively and at best only form simple physical dispersions Mix, note that there is a significant chemical bond forms between the minerals and the continuous phase. Such dispersions are usually metastable, with the mineral tends to separate from the continuous phase.

It has now been found that by superficial coating of the preconditioned surface of these minerals by chemical Reaction with organosilanes the disadvantages mentioned above can be eliminated.

The technique of conditioning these minerals by making them available free hydroxyl (SiIanol) groups to react with Organosilanes have been reported in the art. See FR-PS 2 098 467, issued February 14, 1972. According to this technique are the stratified minerals, which consist of alternating layers of Magnesium oxide and silicon dioxide are built up, the simultaneous action of organosilanes in concentrated mineral acid solution exposed. The effect of this solution on the layered mineral is that, through the action of the strong acid, the Magnesium oxide layers leached out and the alternating silicon dioxide intermediate layers exposed to the accompanying chemical reaction with the organosilanes, the process is continued through the entire stratified mineral system. The procedure results in the elimination of most, if not all, of the magnesia layers and leaves the alternating silicon dioxide layers, separated by layers of chemically converted Organosilane. The implementation is in-depth

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Reaction caused by the diffusion rate of the acid and The organosilane in the mineral body is controlled by what is in the required use of a large excess of concentrated acid, long reaction times and elevated temperatures reflects.

The overall result of these combined reactions is that rather than superficial acid leaching, i.e. removal the outer octahedral magnesium oxide layer and subsequent surface reaction of the exposed silanol groups in the surface with the organosilane, that described in the prior art Reaction goes in depth and most of all magnesia (or isomorphic substituted metal) is removed and leaves an amorphous silicon dioxide residue. This pseudomorphic silicon dioxide, which lacks a crystalline structure, is brittle and has little or no mechanical strength itself. According to the previous technology, this material is a definite one Organo-mineral polymer in contrast to the superficially coated crystalline minerals of the present invention.

The invention proposes organosilane-coated phyllosilicate and amphibole minerals and methods of making the same before. The products obtained according to the invention can after End use can be divided into two broad classes: products which have thermally and chemically stable oleophilic surfaces, and Products with surfaces that have additional chemical bonds with reactive sites within certain plastics and capable of forming elastomers.

Those phyllosilicate and amphibole minerals which have been made oleophilic according to the invention have proven to be extraordinary Suitable additives for regulating the flow behavior of oil-based liquids used in oil and gas wells as a gelling agent in grease and varnish approaches, Tried and tested as a reinforcing agent for rubber and elastomer compounding and as fillers for polyolefin resins and the like.

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Those phyllosilicate and amphibole minerals, their surfaces according to the invention were placed in the state, chemical bonds Forming with reactive sites within plastics and elastomers are particularly suitable for improvement mechanical properties, dimensional and thermal stability and moisture resistance of the refined Composite masses based on phenolic, epoxy, acrylate and vinyl resins as well as both sulfur and peroxide hardened Elastomer systems.

Oleophilized minerals, particularly chrysotile, have been found to be particularly effective in high temperature environments. Without being oleophilic, chrysotile has only limited use in oil thickening because of its affinity for water. Because such systems are exposed to elevated temperatures, chrysotile tends to become wetted by water in the presence of moisture to become, to agglomerate or to separate from the system. By changing the surface properties of the chrysotile after oleophilic, this material can be used effectively in oil systems up to temperatures above 177 ° C. The invention relates to also a process for the production of such minerals with modified surface by a preliminary superficial Acid leaching of the mineral and subsequent condensation with an organosilane.

According to the invention, the mineral is superficial acid leach exposed to dilute acid to form the outer octahedral layer of mixed magnesium, aluminum or iron oxides , which is characteristically present on the surface of such minerals, to dissolve and remove. This implementation exposes silanol groups on the outer silicate layer, so that they become accessible for the formation of silicon-oxygen-silicon-carbon bonds by condensation with an organosilane during a subsequent reaction step. The superficial acid leaching is done with. dilute acid, preferably a mineral acid such as hydrochloric acid or sulfuric acid, under conditions under which the basic structural integrity of the mineral body is preserved.

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In all of the chrysotile this acid leaching takes place with dilute Acid under ambient temperature conditions accompanied by light Stir for times up to about 3 hours.

The conditioned mineral is subsequently combined with the desired Organosilane is coated by mixing these ingredients in the presence of a water-miscible coupling agent such as isopropyl alcohol mixes together. The coating reaction is carried out after the leaching action of the acid has been adjusted by adding of alkali to the slurry obtained from the aforementioned acid leaching or by filtering and washing the acid leaching one Minerals.

The individual components and method steps of the invention are described in detail below.

Minerals

Phyllosilicate and fibrous amphibole minerals, which according to the invention are suitable for modification, are selected from a class of sheet minerals that are characterized by the presence of octahedral Layers containing magnesium, aluminum and / or iron oxides and tetrahedral silicon dioxide layers are marked are. The preferred mineral is a phyllosilicate called chrysotile, a common form of asbestos. · Although chrysotile is the preferred starting material, fibrous amphiboles such as crocidolite, amosite and attapulgite can be used as well as other phyllosilicate minerals such as biotite according to the invention can be used.

Silane modifiers

According to the invention, phyllosilicates or fibrous amphiboles are modified by reaction with organosilanes. These organosilanes are characterized by one of the following two structures:

structure R. I. I. - Si - G ■ R ¹ Y 9817 60 / 1276

wherein G is a hydroxyl group or a group hydrolyzable to hydroxyl, for example alkoxy or halogen; Y is an alkyl group having 1 to 20 carbon atoms, a phenyl group or an alkyl-substituted phenyl group, it being possible for the alkyl groups to contain a total of 1 to 12 carbon atoms; and R and R ^{1 are} independently of one another radicals selected from the group consisting of the radicals of G and Y and hydrogen. Or:

StructureJEI

R.
G-Si-Z

R ¹

wherein G is a hydroxyl group or a group hydrolyzable to hydroxyl, for example alkoxy or halogen; Z is an alkyl group with 1 to 20 carbon atoms which carries a functional group such as amino, oxirane, mercapto or acryloxy and is capable of forming chemical bonds with reactive sites in polymers or prepolymers, or an allyl or vinyl group and R and R ¹ from the group: radical G, radical Z, hydrogen, alkyl having 1 to 20 carbon atoms, phenyl and alkyl, where the alkyl groups can contain a total of 1 to 12 carbon atoms.

According to a preferred embodiment of this invention, the modification of the chrysotile is aimed at this mineral to impart oleophilic properties. It has been found that this is most effectively achieved by using organosilanes, selected from the class having structure I wherein Y is an alkyl chain of 2 to 18 carbon atoms. In particular, methyloctyldxethoxysilane has proven to be a preferred material for oleophilizing the surface of chrysotile fibers proven. Methyldodecyl diethoxysilane, decyltriethoxysilane, octyltriethoxysilane and heptyltrimethoxysilane are also available desirable agents for imparting oleophilic properties.

According to a further embodiment of the invention, a modification Chrysotile sought to make this mineral to implement with reactive sites within the structure of certain

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To enable types of polymers, copolymers, prepolymers, elastomers and resins, e.g. resins of the phenolic, epoxy and urethane types. This is effectively achieved by coating the mineral according to the teachings of this invention with organosilanes of structural class II, wherein Z is the 3-aminopropyl group} in polymers, Copolymers and elastomers based on isoprene, butadiene, butadiene-acrylonitrile or ethylene-propylene-diene are obtained for example effectively using organosilanes of structure II, wherein Z is the 3-mercaptoethy1 group; and at Polyolefins, such as polymers based on ethylene, propylene, isobutylene and the like, or polymers based on vinyl derivatives, such as vinyl acetate, methyl methacrylate, vinyl chloride, vinyl ethers and the like, can be used in the present invention can be achieved by organosilanes belonging to structure II, where Z is a vinyl or allyl group.

Acid leaching of minerals in preparation for the coating procedure

According to the technique of the invention, the outer octahedral Layer of magnesium, aluminum and / or iron oxides can be eliminated by acid leaching in order to generate free hydroxyl groups Reaction with alkoxy groups of the silanes available. As a leaching agent is a mineral acid such as hydrochloric acid or Sulfuric acid most suitable, although other acids, which are soluble salts of the metal oxides in the outer octahedral Layer form, such as nitric acid and acetic acid, are also used Can be.

Extreme reaction times and temperatures should be avoided for the purpose of regulating the leaching in such a way that only the surface layer consists of magnesium, iron and / or aluminum compounds Will get removed. Typically 0.3 to 0.5 parts by weight of H ^ SO ^ in about 10 parts of water upon reaction with 1 part chrysotile at a temperature of about 15 to 27 ° C and a time up to 3 hours usually a suitable superficial Leaching and thereby enable the formation of a satisfactory bond between the organosilane and the mineral surface without noticeable degradation of the basic structure

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nature of the mineral, as seen from the X-ray diffraction pattern of chrysotile before and after such a typical leaching act becomes clear.

The leaching operation can be carried out in a conventional liming device with moderate agitation. After completion of the surface leaching Preferably, sodium or potassium hydroxide is added to raise the pH of the reaction mixture to a value in the range of 2 to 6.5. Bies serves to delay an undesired further leaching and to increase the pH of the mixture to set a suitable range for the subsequent surface reaction with the selected organosilane.

Implementation of the conditioned mineral with silane -

In accordance with the preferred method of this invention, pH ^ graded aqueous suspension of the superficially acid-leached mineral an organosilane, preferably dissolved in a suitable, water-miscible solvent, added with stirring.

The organosilanes are used in amounts of about 0.5% to about 1.0%, based on the weight of the surface-conditioned mineral to be treated. In the special case of a ghrysotile mineral, 3 to 10 # silane can advantageously be used, the optimum amount being around 5 #. When using excess organosilane, some of the excess can polymerize if the silane contains 2 or 3 groups such as G in structure I and II, and dimerize if the silane has 1 such group. This polymer or dimer can deposit on the surface of the mineral and have a disruptive influence on the subsequent processing.

The organosilanes can be added to the aqueous mineral slurry without dilution. Especially if that Organosilane has limited water miscibility, it is $ © - but advantageous to add it in the form of a solution in a water-miscible coupling agent. Methyl, ethyl and isopropyl alcohol and acetone have been found to be suitable coupling agents

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proven. " ax disperse the silane in water and stir result in a homogeneous mixture »in which the silane for conversion, with the conditioned mineral surface stands. Usually about 3 to 6 times the weight of coupling agent is used compared to the organosilane.

The organosilane is added to the aqueous mineral slurry, which is typically about 4 to 16 hours at about room temperature is stirred. Desirably, the temperature of this reaction is kept as low as possible in order to self-polymerize of organosilanes to a minimum, which tend to enter in the presence of water, especially in higher concentrations and elevated temperatures.

After the reaction has ended, the mineral is separated off from the aqueous phase. Organosilane, which is added in excess had been and self-polymerized, can optionally by Wash with a suitable solvent (such as water, isopropyl alcohol or benzene). The treated mineral is then dried and pulverized at about 1o4 - 121 ° C.

In accordance with an alternative mode of operation of this invention, the pH adjusted aqueous slurry of the surface-leached mineral is separated from the aqueous phase, dried at about 104-121 ° G, and pulverized. The powdered acid-leached mineral is dispersed in a non-aqueous solvent such as methanol or isopropanol or in a hydrocarbon solvent such as heptane or benzene, and the organosilane is added to the mineral slurry without dilution. The mixture is typically stirred at temperatures up to reflux for about 1 to 8 hours, after which the mineral is separated from the liquid phase. Organosilane, which was added in excess and self-polymerized, can optionally be removed by washing with a suitable solvent (such as hexane or acetone). The treated mineral is then dried and pulverized at about 1o4- - Λ2.Λ C.

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-11- Example 1

According to the invention, chrysotile asbestos has been made more oleophilic for the purpose of granting Surface properties treated as follows: To a dilute sulfuric acid solution, consisting of 300 cnr water and 9 g 98 # iger sulfuric acid was composed, 25 g of chrysotile with an average fiber length ratio (length / diameter) of about 2oo to 1ooo and dispersed on a Hamilton Beach mixer Stirred for about 3 hours at ambient temperature (21-24 C). To this mixture was added 10 cnr 50 # strength aqueous NaOH to adjust the pH of the mixture to about 6.5. A solution of 2.5 g of methyloctyl diethoxysilane dissolved in 1o cnr of methanol was added to the stirred mixture and 16 hours at ambient temperature continued stirring to complete the reaction. The superficially reacted chrysotile was separated off by filtration, washed with water and air-dried at about 110 ° C for 2 hours. Finally, the dried product lasted about 20-3o seconds ground at about 18,000 rpm in a Waring blender.

Example 2

According to the invention, chrysotile asbestos was treated as follows for the purpose of imparting oleophilic surface properties: 300 g of chrysotile with an average fiber length ratio (length / diameter) of 200 to 1000 were dispersed and stirred on a Hamilton Beach mixer for about 3 hours at ambient temperature (21-24 ° C). To this mixture was added 2o cnr of 50% aqueous NaOH to adjust the pH of the mixture to about 6.5. A solution of 3o g Octyltriäthoxysilan dissolved in 9o g of isopropanol, was added to the stirred mixture, the stirring was continued for 16 hours at ambient temperature (21-24- ⁰ C) until completion of the reaction. Chrysotile reacted on the surface was separated off by filtration, washed with water and air-dried at about 110 ° C. for 16 hours and ground for about 20-3o seconds at about 18,000 rpm in a Waring mixer.

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-12- Example 5

According to the invention, chrysotile asbestos was treated as follows for the purpose of imparting oleophilic surface properties: In a dilute hydrochloric acid solution, which was composed of 160 cm of water and 40 cm of 37% hydrochloric acid, 200 g of chrysotile with an average fiber length ratio (length / diameter) of 200 to 1ooo dispersed and stirred in a Hamilton Beach blender for about 1/2 hour at ambient temperature (21-24- ⁰ C). The surface washed chrysotile was separated by filtration, washed with water and air dried at about 104 ° C for about 16 hours and ground in a mortar. To 100 cubic meters of heptane were added 20 g of the surface-washed, comminuted chrysotile and 2 g of methyldodecyl diethoxysilane. The mixture was refluxed and stirred on a magnetic stirrer for 6 hours. The superficially reacted chrysotile was separated off by filtration, washed with heptane and dried at ambient temperature (21-24 ° C.) for 16 hours at about 110 ° C. for 2 hours.

Example 4

The oleophilic produced by the procedures of Examples 1, 2 and 3 Surfaces were confirmed by placing 1o g of the corresponding reaction product in 35o of a mixture of 95 Parts of diesel oil and 5 parts of water (parts by volume) dispersed. In each case the product formed a stable one in this medium Dispersion, whereas untreated chrysotile asbestos fibers, which were subjected to the same test procedures, are wetted by the water would clump together and fall out of the liquid.

Example 5

The oleophilic properties imparted to the chrysotile according to the invention were using the same as a gelling agent evaluated in an oil slurry and compared to another type of conventional gelling agent used in such systems. The base sludge used for this evaluation was a

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2ο, 8 kg / 1 oil sludge from the Superior Oil Company, D.O. McMann ^ 1, Gonzales County, Texas. To this JTeldschlamm for laboratory tests To prepare, the mud was passed through a 6o mesh (ο, 25 mm) sieve and then kept at 191 ° C for 16 hours Rotate heat aged. This procedure dramatically dilutes the system and makes it susceptible to treatment with a gelation additive. The sludge was then in 0.12 m equivalents divided and treated with the additives with shear mixing at 60 volts for 10 minutes on a Hamilton Beach mixer. The rheological properties were measured at 66 ° C and the samples then at 191 ° C with rotation for 16 hours heat aged. After cooling to room temperature, the samples were shear mixed for 10 minutes at 60 volts and the flow behavior measured again at 66 ° C. The following table summarizes the results of this test.

Table I.

Additional conc Aging o, 454 kg / immediately AV PV YP Gel firm 29 m ^ tration o, 12 rsP 16 hours (cps) (cps) (o, 454 speed 4th at 191 C. kp / 329 (at first/ immediately m ² ) 1o min.) 6th Blank sample 0 16 hours (o.454 kp / 1o at 191 C. 9, i 41 37 7th 3 / 16 Asbestos 6 41 38 6th 4 / immediately 72 65 14th 5 / Asbestos, about 16 hours
at 191 G 36 pulled m. methyl- I00 85 29 8th / 32 octyl diethoxy silane, ex. 1 6 immediately Asbestos, about 16 hours
at 191 C. 148 Ho 75 29 / 37 pulled m. octyl 121 97 47 17 / 29 triethoxysilane immediately Ex. 2 6 16 hours
at 191 C. 8th 7th Organophilic clay 139 I06 65 27 / d. Benton class 6 145 114 59 18 / 7o 60 2o 9 / 47 44 6th 4 /

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These data show that the silane-coated asbestos materials are very effective in gelling oil sludge.

Example 6

Chrysotile asbestos has been treated according to the invention to give the mineral surface to form additional chemical bonds with reactive sites in resins of the phenolic, epoxy and urethane types to enable: In a dilute hydrochloric acid solution, which was composed of 24-OO cnr water and 600 cnr 37 # hydrochloric acid, 300 g of chrysotile were dispersed with an average fiber length ratio (length / diameter) of 2oo to 1ooo and on one Hamilton Beach mixer stirred for about 1 hour at ambient temperature (21-24 ° C). The surface washed chrysotile was separated by filtration, washed with water and dried at about 11o C for 16 hours and about 2o-3o seconds in one Waring mixer ground at about 18000 rpm. Heptane became 100 cnr 40 g of the surface-washed, ground chrysotile and 4 g of 3-aminopropyltriethoxysilane were added. The mixture was on a Magnetic stirrer dispersed under reflux for 4 hours and stirred. The chrysotile reacted on the surface was separated off by filtration., Washed with heptane and air-dried for 1/2 hour at about 110 ° C.

The fixed nitrogen content of the washed and dried product was determined by the Kjeldahl method to o, 38 wt -.% Determined. A similar analysis with the unreacted chrysotile asbestos showed a nitrogen content of o, o #.

Example 7

Chrysotile asbestos additional to the mineral surface to form chemical bonds with reactive sites in resins has been inventively treated as follows to enable the phenolic and epoxy type: In a dilute hydrochloric acid solution, the 37 # is ^it composed of 5oo cnr water and 5o CNP hydrochloric acid were 5o g of chrysotile with an average fiber length ratio (length / diameter) of about 2oo to 1ooo dispersed and then on a Hamilton Beach mixer for about 3 hours at ambient temperature

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temperature (21-24 ° C) stirred. To this mixture 5 cnr were added aqueous sodium hydroxide was added to adjust the pH of the mixture to about 6.5. A solution of 5 g of ß-3 »4- (Ep oxy cyclohexyl ) ethyltrimethoxysilane, dissolved in 15 cnr isopropyl alcohol, was added to the stirred mixture and stirred an additional 16 hours at ambient temperature to complete the reaction. The superficial reacted chrysotile was separated off by filtration, washed with water and air-dried at about 11 ° C. for 16 hours. Finally, the dried product was ground in a Waring mixer for about 30 seconds at about 1800 rpm.

The fixed carbon content of the washed and dried product was found to be 4.16 wt .- ^ by the combustion method certainly. A similar analysis with the unreacted chrysotile asbestos showed a carbon content of 0.21 #.

Example 8

According to the invention, chrysotile asbestos was treated as follows in order to obtain the Mineral surface for the formation of additional chemical bonds with reactive sites in resins of vinyl acetate, methyl methacrylate, To enable vinyl chloride, vinyl ethers and the like: In a dilute sulfuric acid solution, which is made up of 1000 cnr Water and Jo er composed of 98 # iger sulfuric acid, were 100 g of chrysotile with an average fiber length ratio (length / / diameter) of about 2oo to 1000 are dispersed and then on a Hamilton Beach mixer for about 3 hours at ambient temperature (21-24 ° C) stirred. The pH of this mixture was increased to 6.5 set and the solution of 1o g of methylvinyldichlorosilane in

5o cnr isopropyl alcohol added; the pH of this mixture was readjusted to 6.5 and stirred for about 16 hours at ambient temperature continued to complete the implementation. The superficially reacted chrysotile was by filtration separated, washed with water, washed with methanol and air-dried at about 110 ° C. for 16 hours. In the end it was the dried product for about 30 seconds at about 18,000 rpm ground in a Waring mixer.

The fixed carbon content of the washed and dried

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th product was determined by the combustion method to 1.1 wt -.% determined. A similar analysis with unreacted chrysotile asbestos showed a carbon content of 0.21 %.

Example 9

Attapulgite, called Attagel 5o, the Engelhard Minerals and Chemical Company became more oleophilic for the purpose of granting this invention Surface properties treated as follows: To a dilute sulfuric acid solution, which is made up of 400 cnr water and 12 g-98 # iger Composed of sulfuric acid, 40 g of Attagel 5 ° were given and stirred on a Hamilton Beach mixer for about 3 hours at ambient temperature (21-24 ° C). To this mixture were 4 cnr 50 # aqueous sodium hydroxide is added to adjust the pH of the Adjust mixture to about 6.5. A solution of 4 g of octyltriethoxysilane, dissolved in 12 g of isopropyl alcohol, was stirred Mixture set and stirring 16 hours at ambient temperature continued to complete the reaction. The attapulgite reacted on the surface was separated off by filtration and washed with water and air-dried at about 14 ° C. for 16 hours. Eventually the dried product was about 2o-3o Milled for seconds at 18,000 rpm in a Waring mixer.

The reaction was confirmed by measuring the fixed carbon content of the washed and dried product by the combustion method to be 4.5 wt .- ^. A similar analysis with unreacted attapulgite showed a carbon content of 1.1 %. The materials were in a mixture of 332 enr diesel 3 ■

oil and 18 cnr water and the theological properties measured in a Fann viscometer.

Table II

Concentration Viscosity Viscosity Gelfestig- (o, 454 kgA at 600 rpm at 300 rpm

o, 12 no) (cps) (cps) (beginning / 1o

Minutes) (o.454 kp / 9.29 m ^d )

not correct s et z-
ter attapulgite 3o 2o 12th 1 / 2 implemented
Attapulgite 3o 27 17th 3 / 6th 60981 7/1276

Example 1o

The oleophilic surface properties imparted to chrysotile asbestos were demonstrated by compilation and evaluation of two sample fats using identical amounts of gelling agent, one of which was the unmodified ghrysotile asbestos that was used to make that described in Example 2 oleophilic derivative was used, and the other the reaction product of the surface acid-leached chrysotile asbestos with octyltriethoxysilane, which is described in Example 2. 81 g of the product obtained in Example 2 were 5 minutes ground in a Waring mixer at about 18,000 rpm, then for 369 g of mineral oil 300 S.U.S. set evenly with a spatula incorporated and finally passed through a Morehouse Mill with a distance of 0.05 mm. The second fat was then made in the same way using unmodified chrysotile asbestos. The two fat samples were then characterized as follows:

Table III

Non-Machined Drip Water

works Pono-H ^ a-Mnn ³ * P ^un ^ * firm- penetration * - ^ stration keit gg

Fat from superficial

converted chrysotile 273 275 26o + C

Fat from unreacted

tem chrysotile 3o1 3I6 249 ^ C fails

χ ASTM 217
sä MIL-6-3278

Example 11

The chrysotile asbestos imparted oleophilic surface properties and further the water-resistant nature of polymer matrices using such treated mineral fibers as they are taught in accordance with the invention has been demonstrated below Compilation and evaluation of three nitrile elastomers using identical amounts of reinforcing agents, where one of the for the preparation of the oleo-

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phile derivative used unmodified chrysotile asbestos and the other was the reaction product of the surface acid leached chrysotile asbestos and octyltriethoxysilane found in Example 2 is described; the third was carbon black, designated Type N-326, which is commonly used as a nitrile rubber reinforcing agent is used. 5 ° parts of that obtained in Example 2 Product were ground, vulcanized and treated under standard conditions with 100 parts of nitrile rubber and 12 parts of plasticizers, Accelerators and hardeners normally used in such approaches. The second and third samples were similarly using the unmodified Chrysotile asbestos in one case and type F-326 carbon black in the other instead of the silane-coated asbestos product made from example 2.

These three samples were then tested for moisture resistance according to the following procedure. Cut from hardened panels Tensile strength strips were weighed and placed in an autoclave in a steam environment of 2o5 G and 21 kp /

/ cm overpressure suspended. The strips were then removed from the autoclave and the surface moisture removed. The plates were then weighed immediately to determine moisture uptake to determine; the following results were obtained:

Table IV

Moisture increase # based on strip weight

Rubber with superficially converted chrysotile from Example 2
pounded - 1.75

Rubber, with unreacted

Chrysotile compounded +9.2

Rubber compounded with N-326 carbon black + 5 »6

Example 12

To the applicability of the materials according to the invention as reinforcing agents for various resin polymers and the ability

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such materials to reduce water adsorption such Samples were used to illustrate filled polymer prepared as follows: 3.3 grams of Shell R-15 epoxy resin was added with 0.5 g enhancer; and 0.67 g dipropylenetriamine curing agent mixed. This mass was cured at 38 ° G for 16 hours. the Water adsorption tests were carried out according to ASTM D 57o-63. The results are summarized in Table V:

Table V Reinforcements $ Weight Gain

unreacted asbestos 1.82

Mass from example 2 1.15

Mass from example 6 1.57

Mass from example 7 1.22

Similar results were obtained with a polymer compound of 8, ο g polyester resin, 2, ο g reinforcing agent and ο, 4 g methyl ethyl ketone peroxide, which were cured overnight. The results are given in Table VI.

Table VI Reinforcements $ Weight Gain

unreacted asbestos o, 575

Mass from example 8 o, 369

Claims

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Claims (18)

rti. Claims 1. Process for conditioning a layer mineral from the class of phyllosilicates and fibrous amphiboles with preparation the surface of the same for coating with organosilane compounds, characterized in that the mineral with leaches dilute acid under reaction conditions which only dissolve a superficial octahedral layer of the Metal oxide from the mineral are sufficient and silanol groups of the Expose minerals. 2. The method according to claim 1, characterized in that chrysotile asbestos is used as the layer mineral. 3. The method according to claim 1, characterized in that Attapulgite is used as a layer mineral. 4. The method according to claim 1, characterized in that is leached with sulfuric acid. 5. Process for coating a layer mineral from the Group of phyllosilicates and fibrous amphiboles with an organosilane, characterized by the following steps: (a) Leaching of the mineral with a dilute acid under reaction conditions which are only sufficient to dissolve a superficial octahedral layer of the metal oxide from the mineral and silanol groups of the mineral y (b) stopping the leaching process according to a); uncover (c) subsequent reaction of the tempered mineral with organosilane; and (d) Recovery of the obtained silane-coated mineral. 6. The method according to claim 5 »characterized in that chrysotile asbestos is used as a layer mineral. 7. The method according to claim 5 »characterized in that methyloctyldiathoxysilane is used as this organosilane. 8. The method according to claim 5 »characterized in that the leaching process by adding alkali to the mixture of acid and 6 ü 9 8 1 7/1276 Mineral is stopped to increase pH. 9 · The method according to claim 5, characterized in that the leaching process is prevented by physical separation of the mineral and the acid. 10. Product of a crystalline mineral layer structure the group of phyllosilicates and fibrous amphiboles with a superficial coating of an organosilane, the is chemically bonded to the surface of the mineral structure. 11. Product made of a crystalline mineral layer structure the group of phyllosilicates and fibrous amphiboles, whose superficial octahedral oxide layer has been removed is, with a layer of organosilane, bonded to the crystalline mineral structure through oxygen-silicon bonds is. 12. lettuce made from an oil and gelling agent, the The gelling agent is the product according to claim 11. 13. The method according to claim 5, characterized in that the organosilane used is 3-aminopropyltriathoxysilane. Drilling fluid from an oil mud and a gelling agent, composed of chrysotile asbestos coated with an organosilane. 15. drilling fluid according to claim 14, characterized in that that this chrysotile asbestos has been coated with Methyloctyldiäthöxysilan. 16. drilling fluid according to claim 14, characterized in that that this chrysotile asbestos has been coated with Oetyltriäthoxysilan. 17 · Product made from a hardened resin polymer and a reinforcing agent composed of earysotile asbestos coated with an organosilane. 18. Product made from an elastomer and a filler which 609817/1276 is composed of chrysotile asbestos coated with an organosxlan. 609817/1276