WO1989008621A1

WO1989008621A1 - Product in which the surface of the particles is partly hydrophilic and partly hydrophobic

Info

Publication number: WO1989008621A1
Application number: PCT/FR1989/000107
Authority: WO
Inventors: Christiane Casagrande; Madeleine Veyssie; Pierre-Gilles De Gennes
Original assignee: Centre National De La Recherche Scientifique (Cnrs
Priority date: 1988-03-15
Filing date: 1989-03-15
Publication date: 1989-09-21
Also published as: FR2628731A1

Abstract

Solid particles having combined surface tension properties with regard to water and/or oil, characterized in that they are based on aluminium and/or silicon oxides, and in that one part of the free surface of each particle presents hydrophilic properties and the other part hydrophobic properties. Processes for their preparation and applications for said particles.

Description

PRODUCT OF WHICH PARTICLE SURFACE IS PARTIALLY HYDROPHILIC AND PARTIALLY HYDROPHOBIC

The present invention relates to solid particles whose surface is partially hydrophilic and partially hydrophobic, a process for their preparation, and the applications of said particles. For more than 20 years, attempts have been made to solve the problem of preparing beads which simultaneously have hydrophilic properties and hydrophobic properties, that is to say having mixed surface tension properties with respect to water and / or oil. US-A-3,222,204 describes the treatment of the surface of glass microbeads with an oleophobic fluorocarbon agent. The beads thus treated exhibited buoyancy allowing them to remain visible on the surface of the reflective coating for which they were developed, while remaining well attached in the binder layer of said reflective coating.

French patent application FR-A-2 579 608 proposes to treat glass microbeads uniformly over their entire surface with two different substances. The first substance is intended to make the beads hydrophobic while retaining their oleophilic nature: it is essentially a silane. The second substance is intended to make the microbeads hydrophobic and oleophobic and consists, as in the document cited above, of a fluorinated hydrocarbon.

Finally, European patent EP-A-0 056 771 proposes a third solution to the problem, through an improvement in the behavior of glass microbeads in a retroreflective paint. This document recommends the use of a mixture of two different types glass microbeads. The first type of beads has undergone a treatment similar to that described in the document US-A-3,222,204 cited above. The second type of beads was treated with a hydrophobic agent such as a silane.

The solutions proposed are only compromises which are not entirely satisfactory and none of the cited documents envisages the preparation of solid particles of which a part of the surface is hydrophilic, the other being hydrophobic. The Applicant now proposes such a type of particle. The solid particles according to the invention, having mixed surface tension properties with respect to water and / or oil, are characterized in that they are based on ¹ aluminum oxides and / or 5 silicon, in that part of the free surface of each particle has hydrophilic properties and the other part of the hydrophobic properties.

The following figures are intended to illustrate the invention more precisely. 0 FIG. 1 represents a series of three cour¬ bes illustrating the concentration of protective collodion as a function of the average diameter of glass beads to be treated, the curves correspond to a different number of layers of collodion. 5 The set of FIGS. 2 to 5 represents microphotographs of breath figures, obtained by concentration of water vapor on surfaces having undergone different treatments.

Figure 2 is a reproduction of the micro-0 photograph of a glass plate of which a part of the surface is hydrophilic, 1 ^"-Other portion having been hydrophobized.

FIG. 3 is a reproduction of the micro-photograph of the hydrophilic hemisphere of a ball se- - ^• - 'Ion the invention. FIG. 4 is a reproduction of the micro-photograph of the hydrophobic hemisphere of a ball according to the invention.

FIG. 5 is a reproduction of the micro¬ photograph of a ball according to the invention, under an incidence allowing a part of each hemisphere to be seen.

The detailed description which follows is intended to underline the advantages and characteristics of the invention.

By free surface is defined the outside surface of the particles.

It is advantageous to use silica particles. Particles consisting essentially of one or more aluminosilicates such as glass, sa¬ phir, give good results. Particularly preferred are glass particles.

The invention has in particular the advantage of not requiring the use of particles of homogeneous particle size and / or of regular shape. The particles according to the invention can have a spherical, ovoid, for example, or even random shape.

Regardless of their shape, the particles can be hollow.

The average particle size of the particles according to the invention is between 10 and 150 μα, preferably between 25 and 100 μm.

The hydrophilic surface of the particles, respectively hydrophobic, is at least equal to that of a shell, the rest of the surface of the particle being hydrophobic, respectively hydrophilic. The term “cap” is understood to mean a surface portion of between 10 and 50% of the total free area. Advantageously, the hydrophilic and hydrophobic surfaces each occupy approximately half of the surface of each particle.

Particularly advantageously, the particles are beads, substantially one hydrophilic st hemisphere, and the other hydrophobic hemisphere.

According to a variant of the invention, the particu¬ are balls whose caps are hydrophilic, respectively hydrophobic, the equatorial part then being hydrophobic, respectively hydrophilic.

The invention also relates to a process for the preparation of the previously described solid particles.

The particles are prepared according to a surface treatment process comprising the following steps:

- protection of a free surface portion of the particle corresponding at least to that of a cap;

- grafting of a hydrophobic group on the remaining unprotected part of the particle;

- elimination of protection;

- rinsing of the particles thus obtained. Advantageously, the surface on which one does not want to carry out grafting is protected by the deposit thereon of a substance which must have the following five characters:

- very good adhesion to the substrate to be protected;

- easy solidification; - absence of solubilization during the treatment of grafting on the unprotected part;

- solubilization after said treatment;

- no alteration of the protected surface. Cellulosic derivatives give good results. Among them, a cellulose varnish such as collodio (cellulose nitrate) can be used in a particularly advantageous manner. Indeed, in addition to the qualities required above, the collodion is easily available and inexpensive. Advantageously, the particles to be treated can be spread out in a monolayer in a collodion solution in alkyl acetate, so that they are there substantially half submerged.

The larger the particles, the greater the concentration of collodion in amyl acetate. According to a preferred implementation of the method, one or more layers of identical concen¬ tration solution are spread in collodion, without waiting for the solvent to evaporate between each layer deposition. Then, the particles are projected onto the collodion surface. FIG. 1 is a series of curves illustrating the diameter of the particles immersed approximately half, in the collodion solution, as a function of the concentration of the collodion solution spread out in one, two or three successive curves:

concerns a single layer of collodion

******** concerns two layers of collodion concerns three layers of collodion

The average particle diameter d is expressed in μm. The collodion concentration is expressed as% by weight of the collodion in amyl acetate.

The hydrophobic groups grafted onto the hydrophilic surfaces are chosen from hydro-carbon radicals, hydrofluorine radicals, silanes, linear or branched.

Hydrophobic groups preferably have 4 to 18 carbon atoms. A particularly preferred silane is octadecyltrichlorosilane. After the grafting treatment, the particles are washed with a solvent for the protective substance, said solvent not having to attack the hydrophobic surface. In the case of collodion protection, methanol is a particularly suitable solvent. Particles now having part of their hydrophilic surface and part of their surface hydrophobic, are thoroughly rinsed with water.

A variant of the process consists in rendering a portion of the surface of uniformly hydrophobic particles hydrophilic. It is possible, for example, to strip a portion of the surface of uniformly silanized glass particles.

Advantageously, the particles are floated on ^' water to protect the submerged portion from pickling.

The etching of the non-submerged portion of the surface is carried out by the action of a stream of oxygen and of ultraviolet radiation: it then suffices to collect the treated particles by simple sieving, and to dry them.

Such a variant of the process according to the invention is particularly advantageous insofar as. its implementation can be done continuously.

The particles thus obtained by the implementation of the method or its variant have a specific behavior at the oil-water interfaces, in comparison with particles which are uniformly hydrophilic or uniformly hydrophobic.

The invention finally relates to the applications of the particles according to the invention.

The use of the particles according to the invention as a solid surfactant is particularly interesting.

The particles according to the invention can, for example, be advantageously used for the stabilization of an emulsion. A first advantage of this use lies in the fact that, after stabilization of the emulsion, the surfactant can easily be recovered by any means (for example by simple sedimentation). In addition, there is no risk of a parasitic reaction between the components of the emulsion and the surfactant according to the invention. A second advantage is that an emulsion can be stabilized with particles having a dispersed granulometry, and any shape.

Another particularly interesting use of the particles according to the invention is the use of the latter for microfiltration. Indeed, surprisingly, said particles allow the scanning of a fluid with low interfacial resistance in the liquid-liquid interstices of an emulsion. For this application, it is preferred to use particles of generally spherical shape. An undispersed particle size of the balls, depending on the size of the body to be filtered, allows a transfer of the latter into the interstices. The particles according to the invention can also be used as a thixotropic agent. In this case, it is preferable to use particles according to the variant of the in¬ vention explained above, namely spheres with little dispersed granu¬ lometry, comprising a hydrophilic equatorial zone, respectively hydrophobic, and two hydrophobic caps, respectively hydrophilic.

Such particles form linear chains in a composition at rest, increasing its viscosity, which are easily undone during agitation with the consequence of a reduction in viscosity.

Other characteristics and advantages of the present invention will appear on reading the following example.

EXAMPLE Manufacture of beads according to the invention and comparison of their specific properties with glass p-glass or glass beads hy-drop-hobes or hy-drop-hiles on the surface

The starting materials used are glass micro-beads manufactured by the company GLAVEREEL.

The beads having a size dispersion, iso-lé by successive sieving, the fraction of bil¬ whose diameter d is between 40 and 50 microns.

The surface of these beads is hydrophilic due to the Si-OH surface groups. These balls are dispersed in the mono¬ layer state on a collodion film, of thickness d / 2, itself spread, for example in two layers on a glass slide.

The collodion is in solution in amyl acetate at a concentration of about 5% (by weight).

Once the amyl acetate has evaporated, it is checked under a binocular telescope that the beads are actually set halfway up.

This preparation (glass slide, dry collodion film and beads) is then immersed in a chloroform solution and then treated with octadecyltrichlorosilane.

This method has already been used with efficiency in the treatment of flat surfaces, to effect the fixing by covalent bond of the siloxane molecules on the surface SiO sites.

The collodion is then solubilized in methanol, thus releasing the treated beads on half of their surface. Rinse thoroughly with water, then dry.

As a witness, a glass slide is subjected to the same series of operations, part of the surface of which is protected by collodion.

The balls are then subjected to the following tests:

Test # 1

The beads obtained and the control glass plate are subjected to the breath figures test, described by MERIGOUX (Revue Optique Française 16, (1937), 281). This simple test consists in observing, under the microscope, the condensation of water vapor projected on a solid surface. If the surface is hydrophilic, the water tends to wet it completely, and spreads out in broad sheets with ill-defined contours. On the contrary, if the surface is hydrophobic, there appear fine droplets (with a diameter close to 10 μm) whose contact angle with the surface is close to 90 °.

These two situations are illustrated by FIG. 2 which represents a photomicrograph of the reference plane glass slide.

When the population of treated beads is subjected according to the method to the test described above, there are either visible hydrophilic surfaces (FIG. 3), or surfaces of mixed nature, depending on the orientation of the grains. FIG. 5 represents a photomicrograph of a particle according to the invention, at an incidence such that a part of each hemisphere is visible. Test # 2

This test consists in comparing the behavior of the beads according to the invention and that of bil_ = s totally hydrophilic or totally hydrophobic, with an oil-air interface.

The balls treated according to the example have a density equal to 2.5. The oil used has a density of 1.02.

It can be seen that the balls are not immersed. The center C of the spheres is located below the water line L.

The distance h from C to L obeys the following order relationship: h (hydrophobic beads) <h (invention beads) <h (hydrophilic beads) Test N ° 3

Oil and water are placed in three glass containers. In each container, a category of beads was added. The bottles are shaken as standard. In the mixture containing the hydrophobic beads, a common phenomenon of coalescence is observed. The immiscible oily and aqueous phases are instantly reconstituted. In the mixture containing the hydrophilic beads, large pockets of water are observed along the pa¬ king of the container, in which the beads are trapped.

In the mixture containing the beads. - according to the invention, it is found that the latter stabilize drops of water of fairly uniform size (of the order of mm).

Under a binocular microscope, it can be observed that the drops of water thus stabilized are coated in a continuous manner with a monolayer of beads.

The particles according to the invention have the desired original properties, which allows their satisfactory use as a solid surfactant emulsion stabilizing agent, or even as a micro-filation agent.

Claims

1. Solid particles having mixed surface tension properties with respect to water and / or oil, characterized in that they are based on aluminum and / or silicon oxides, and in that a part of the free surface of each particle has hydrophilic properties, and the other part of hydrophobic properties.

2. Particles according to claim 1, characterized in that they are based on silica.

3. Particles according to claim 1, ca¬ characterized in that they are based on aluminosilicates such as glass or sapphire.

4. Particles according to any one of claims 1 to 3, characterized in that they have random shapes.

5. Particles according to any one of re¬ vendications 1 to 4, characterized in that they have a substantially spherical shape.

6. Particles according to any one of claims 1 to 5, characterized in that they have an average particle size of between 10 and 150 μm, preferably between 25 and 100 μm.

7. Particles according to any one of claims 1 to 6, characterized in that they are hollow.

8. Particles according to any one of the re¬ vendications 1 to 7, characterized in that their hydrophilic surface, respectively hydrophobic, is at least equal to that of a cap, the rest of their surface being hydrophobic, respectively hydrophilic.

9. Particles according to any one of the re¬ vendications 1 to 8, characterized in that they affecten the shape of beads, substantially one hemisphere is hydrophilic and the other hydrophobic.

10. Particles according to any one of the re¬ vendications 1 to 6, characterized in that they affect the shape of beads whose caps are hydrophilic, respectively hydrophobic, the éσuatoriale part being hydrophobic, respectively hydrophilic.

11. Method for preparing the particles according to any one of claims 1 to 10 comprising the following steps:

- protection of a portion of the free surface of the particle corresponding at least to that of a cap;

- elimination of protection;

- rinsing of the particles thus obtained.

12. Method according to claim 11, characterized in that the hydrophobic groups grafted on the hydrophilic surfaces are chosen from hydrocarbon radicals, hydrofluorinated radicals, siians, linear or branched.

13. The method of claim 12, caracté¬ ized in that the silane used is 1'adctadécyltrichlorosilane.

14. Method for preparing the particles according to any one of claims 1 to 10, consisting in rendering a portion of the surface of uniformly hydrophobic particles hydrophilic.

15. The method of claim 14, caracté¬ ized in that the particles are floated on water and that the non-submerged portion of the surface is subjected to the action of a stream of oxygen and of an ultra-violet radiance.

1 6. Use of the particles according to any one of claims 1 to 1 5, as a solid surface-active agent, emulsion stabilizing agent or also as a micro-filtration agent.