FR2615195A1 - PROCESS FOR FORMATION OF A POLYMERIC MATERIAL CHARGED WITH A POLYMERIC MATER, FORMED THEREFOR, AND GLAZING MATERIAL FOR INCORPORATING LIQUOR IN A POLYMERIC MATERIAL - Google Patents

Abstract

THE INVENTION RELATES TO THE FORMATION OF POLYMERIC MATRICES CONTAINING AN INORGANIC CHARGE. IT CONSISTS OF ATTACHING THE POLYMERIZATION CATALYST TO THE MATERIAL INTENDED TO BE INCORPORATED AS A CHARGE IN THE POLYMERIZED MATERIAL. THIS LOAD IS PREFERABLY CONSISTING OF GLASS MATERIAL, FOR EXAMPLE GLASS MICROBALLS. THE INVENTION IS PARTICULARLY USEFUL WHEN FORMING RETROREFLECTING FLOOR MARKINGS USING A PAINT WHICH POLYMERIZES.

Description

1.

  PROCESS FOR FORMING A POLYMERIC MATERIAL CHARGED WITH:

  POLYMERIC MATER SO FORMED AND VITREOUS MATERIAL INTENDED

  TO BE INCORPORATED AS A LOAD IN A POLYMER MATERIAL.

  The present invention relates to a method of

  formation of a polymer matrix loaded with inorganic material

  wherein the material to be incorporated as a filler is contacted with polymerizable material and a catalyst for effecting the polymerization of the polymerizable material and thereby forming the polymer matrix. The invention includes a charged polymer matrix formed by this process, and extends to a material to be incorporated as a filler in a

polymer matrix.

  Many polymerizable materials are known, and their use in more and more varied fields extends widely. A considerable interest of this type of materials lies in the fact that they can be used in the fluid or even visco-elastic state to shape them by molding techniques, extrusion; injection, etc ... at controlled temperature. A big number

  of thermoformable resins at moderate or

  This type of technique requires the presence of a polymerization catalyst to initiate the chain reaction which forms a cured article. It is obvious that the success of the polymerization operation, ie the obtaining of a homogeneous polymer mass, requires a homogeneous distribution of the

  catalyst in the polymerizable material.

  It is also common to incorporate a "char-

  ge "in a polymeric material.This operation can be

  performed to modify the mechanical, thermal and

  electrically or simply a polymer, or simply

  to reduce the cost of parts formed from the polymer. It is well known, for example, to incorporate glass fibers, either in the form of individual fibers or in the form of a fiberglass web (which can

  be woven or non-woven), in a polymer matrix.

  Currently, we use more and more loads

  consisting of glassy microbeads. The expression "

  is used herein to designate glass and vitrocrystalline material (i.e., a material obtained by heat treating a glass to introduce a

  crystalline phase). In particular, the use of micro-

  hollow glass is advantageous because it allows to

  manufacture low density parts.

  There are some difficulties in achieving the proper distribution of filler and catalyst in the polymerizable material needed to provide a high quality polymer matrix, especially when the polymerization reaction is quite fast. As an example of the difficulties we may encounter, we can

  mention the case of road marking paints which incor-

  pores, as a filler, glass microbeads intended to make the paint retroreflective,

  to make the marking visible at night. A technique

  As known from US Pat. No. 2,897,732, this technique consists in spreading a polymerizable paint of the polyester-vinylidene copolymer type, to be sprayed on the paint.

  powder polymerization catalyst and then to sau-

  powder the paint with glass beads so that some of them sink into the paint, before its complete polymerization. This technique suffers

  of a number of disadvantages. First, it requires

  site the use of complicated equipment provided with

  three separate heads of material distribution. Second-

  the catalyst, which is by far the most

  expensive, can easily fly off during its

  and therefore be lost. Thirdly, the catalyst is essentially deposited on the surface of the paint, and this gives rise to different levels of polymerization of the paint which lead to the cracking of the paint.

  the surface and a catalyst deficiency in the

  painter of painting. Fourth, although a polymerization

  3. Fast painting is desirable, the faster is the polymerization, the easier it is to obtain the desired distribution of the beads in the thickness of the paint. One of the objects of the present invention is to provide a process for forming a charged polymer matrix, which facilitates a good distribution of the catalyst in the polymerizable material, which allows a rapid action of the catalyst, and which makes it possible to reduce in a certain proportion the amount of catalyst required to

  perform a complete polymerization of the poly-

  merit forming the polymer matrix.

  The present invention relates to a method of

  formation of a polymer matrix loaded with inorganic material

  in which the material intended to be incorporated as a charge is brought into contact with

  polymerizable and a catalyst for carrying out the polymerization

  of the polymerizable material and thereby form the polymer matrix, characterized in that catalyst is attached to the surface of the material to be incorporated as a filler before it comes into contact with the

polymerizable material.

  The implementation of such a method is very simple. In comparison with the mixing of a catalyst and a polymerizable material, it is generally much easier to ensure a good distribution of the filler in the polymerizable material. Since, according to the present invention, the catalyst is attached to the filler, a good distribution of the polymerizable material and the filler involves a good distribution of the catalyst and the polymerizable material. As a result, the catalytic polymerization can be carried out rapidly, efficiently and regularly throughout the entire material. In addition, the amount of catalyst applied to the feed can be

  controlled easily so that the amount of catalyst

  lost is greatly reduced. It has been observed that it is sometimes possible to use less catalyst in the process according to the invention than when using a separate feedstock and catalyst. It is quite surprising that the

  technique of the invention gives rise to a catalytic action

  more effective: indeed, there is every reason to believe that if the catalyst is attached to a material foreign to the polymerizable material, its reactivity towards

of it would be inhibited.

  Advantageously, said catalyst is adsorbed in a coating of fixing agent adhering to the surface of the material to be incorporated as a filler. This makes it possible to fix the catalyst to this material in such a way that it can be stored and handled before being brought into contact with the polymerizable material, without loss of catalyst and without reducing its reactivity with respect to the material to be polymerized. It has been found that a number of materials are capable of forming a strong chemical bond with materials commonly used to charge polymeric matrices and can be used as a carrier.

  catalyst fixation. It is preferred to adhere a compound

  organometallic material to the said material to be incorporated as a filler to act as a fixing agent. Such compounds easily form a bond

  with inorganic materials commonly used

  as a filler, forming a monomolecular or multimolecular layer, and they are capable of binding catalyst to the filler. It is especially preferred that said organometallic compound is selected from silanes, chromium complexes, titanium derivatives or methoxysilyl polymers. Such compounds are particularly effective binding agents and they also have the advantage of promoting coupling between the filler and many highly polymeric materials.

  such as polyesters or polyacrylates.

  This promotes the production of composite materials having high flexural strength. This 5. '. also promotes high abrasion resistance of the load, which is especially important when the polymer matrix is to be used

as road markings.

  Examples of such materials are vinylsilanes (Union Carbide A151),

  methacryloxysilanes (A174 from Union Carbide), styryl

  silanes, Werner-type chromium complexes comprising fumaric acid complexes (Du Pont Volans *), Kenrich isopropyltitanates (TSM2-7, TSM2-11, TTM33, TTAC-39), and special polymers comprising groups

  methoxysilyls (Polyvest 25 * from H ls). (* Trademarks

cial)

  A coating of fixing agent may be applied

  on the material intended to be incorporated in the form

  by different techniques such as immersion

  or any other method of contacting with a liquid reagent followed by drying, or by deposition from a vaporized reagent, for example, in the case of a particulate material to be incorporated as a

  charge, in a fluidized bed. The formation of such a coating

  This may be followed by impregnation of the coating with the catalyst, by contacting the coating with a liquid or dissolved catalyst. In certain preferred embodiments of the invention, the material

  intended to be incorporated as a load is set

  contact with a solution containing the catalyst and a fixing agent to fix the catalyst to the surface of the material, and this is then dried. In this way, the fixing agent and the catalyst are applied in a single step, and the process is therefore very simple and fast. In other preferred embodiments of the invention, said material to be incorporated as a filler is contacted with a suspension containing said catalyst and a fixing agent to

  to fix the said catalyst on the surface of the said material

  re. This technique is even simpler and faster, since the drying step can sometimes be eliminated. For example, a fixing silane can be mixed with,

  As a catalyst, the Interox BP-40-S (trade mark

  ciale) from Peroxyd-Chemie GmbH of Munich, which is a suspension of 40% dibenzoyl peroxide in phthalate. Embodiments of the invention o the

  material intended to be incorporated as a filler shall be

  with an unsaturated polyester to perform the poly-

  merification are preferred. The invention can be used to produce articles of such materials, for example acrylic or urethane-acrylic resins, in the presence of a catalyst at room temperature, using acceleration if necessary. This method can be used to make items from one

  unsaturated polyester dissolved in a copolymeric monomer

  sand, for example metacrylic oligo-urethane resins

  in methyl methacrylate as a solvent

  monomer, or mixed polyester resins and a mono-

  vinyl, acrylic or allylic mother.

  There are different polymerization catalysts

  which make the curing of polymeric materials

  faster and / or possible at lower temperatures. The use of peroxide as a catalyst is often recommended, especially in the polymerization

  unsaturated polyester resins and their copolymers.

  The invention comprises a process in which a peroxide, for example benzoyl peroxide which exists in the form of a powder which is easy to handle, is attached to the surface of the material intended to be incorporated under

form of charge.

  Various materials customarily used for charging polymer matrices may be employed in the process of the invention. Of these, one can

  mention natural minerals such as mica or talc.

  In the preferred embodiments of the invention, however, said material to be incorporated as a filler comprises vitreous material. The use of

  vitreous material has many advantages; in part-

  particular, the vitreous materials intended to be incorporated

  are cheap and easily available.

  they can take many forms and

  dimensions to give the product particular properties.

highly desirable.

  In certain preferred embodiments of the invention, said material to be incorporated as a filler comprises glass fibers. Such fibers may be short individual fibers, or they may be long fibers constituting a veil

woven or non-woven.

  In the preferred embodiments of the invention, said material to be incorporated as a filler comprises glassy microbeads. The vitreous microbeads are particularly useful because their very high degree of spherical symmetry greatly facilitates their mixing with a fluid or viscoelastic polymerizable material, so that the microbeads, and hence also the catalyst, are well distributed in its mass, and because their use gives good flow properties in any molding operation and

  allows a uniform distribution of constraints to the

  of the polymer matrix formed.

  If it is desired to manufacture a low density article, it is possible in this case to use hollow glassy microspheres. However, if it is contemplated that good mechanical strength of the product is greater than low density, solid microspheres will be selected. To obtain a product with the best properties

  mechanics, it may be desirable to use micro-

  vitrocrystalline beads rather than microbeads

  glass, despite their generally higher price.

  The size of the microbeads used as a filler can have a significant effect on the ease of shaping of the charged polymer matrix and / or on the possible properties of that matrix. In the case

  molded plastics, it is usually

  that the average diameter of the microbeads is

  taken between 20 and 50 microns, for example about 44 micrometers. This is due to the effect of the presence of microbeads on the flow properties of the polymerizable material during the molding operation. On the other hand, microbeads & use in paints generally have a mean diameter of between 50 and 650 '

  micrometers, which is advantageous for good

  summers of reflection of the loaded painting. The references

  the average diameter of the microbeads in the present

  cription are references to the average diameter by number

  microbeads, that is, there are as many micro-

  beads having a diameter smaller than this value than microbeads having a larger diameter. Therefore, in preferred embodiments of the invention, the glassy microbeads are chosen in such a way that

  their average diameter is between 20 and 650 micro-

meters inclusive.

  It should be noted that the smaller the surface area

  microbeads, the lower the available surface area

  ble for fixing the catalyst. In the case of resi-

  In the case of casting or molding, where smaller microbeads are generally used, it is sufficient to choose the size of the microbeads according to the amount of catalyst to be added to the polymerizable material.

  which microbeads must be mixed. How-

  In the case of paints or other resins, microbeads are applied to the polymerizable material after it has been layered on a surface.

  it may be desirable to use microbeads

  very large, for example microbeads whose diameter is between 150 and 650 microns, so that the microbeads can more easily sink into the layer of polymerizable material and drive the catalyst to the depths of the layer, 9. despite such larger microbeads have a lower specific surface area and carry for this

  relatively little catalyst.

  Advantageously, at least some of the micro-

  Glassy beads have rough surfaces. Roughness

  surface can be obtained by a treatment technique.

  mechanically, but to obtain the preferred dimension

  microbeads, it is much easier to

  read chemically. For this reason, it is preferred that

  at least glassy microbeads are treated

  by means of a corrosion agent before being coated.

  These corroded microbeads have rough surfaces and therefore larger surface areas than

  polished microbeads of the same dimensions. Such micro-

  rough logs are therefore able to fix more than

  catalyst for the same average diameter. Such a technique

  that chemical attack can result in fixing

  at least 3 times more catalyst on the microbeads.

  This is particularly advantageous when using fairly large microbeads and / or when rapid polymerization is required, and / or when such polymerization is desired at low ambient temperatures, for example when performing ground markings. in winter. Note that microbeads with surfaces

  Roughly lose the reflective properties

  for which they were initially selected

  for road markings. This does not present any incon-

  This is true because it is sufficient to mix such microbeads with uncorroded microbeads carrying the catalyst to impart the desired reflectivity to the label, or with other non-corroded microbeads, as will be described below. This may actually be advantageous in some circumstances since such corroded microbeads can be used to replace white pigment fillers, such as lime or titanium dioxide which may be more expensive. 10. The etching process can be carried out very simply by means of a corrosive medium containing fluorine ions, for example a solution of ammonium bifluoride. However, this is only used to treat solid microspheres because the hollow microspheres may have walls that are too thin to resist

& this treatment.

  It has been mentioned the possibility of mixing glassy microbeads carrying the catalyst with other

  microbeads. In some preferred forms of

  of the invention, vitreous microbeads are coated with

  This material is both oil-repellent and hydrophobic and is incorporated as a filler with glassy microbeads carrying a catalyst. Such a mixture is particularly well suited for use in ground marking because microbeads bearing the

  catalyst can be sprinkled on the liquid paint

  at the same time as the hydrophobic, oleophobic balls: a very simple apparatus is thus used comprising a gun delivering the polymerizable material and a single ball-catalyst projection head. The balls carrying the catalyst will penetrate and mix in the heart of the paint layer while the hydrophobic balls,

  oleophobes remain exposed on the painting layer o-

  they reflect the incident light until they

  eroded by traffic and, at this point, the erosion

  sion will have revealed some of the microbeads that

  the catalyst, which in turn can reflect

chir the light.

  Advantageously, microbllles carrying a catalyst represent between 70% and 90% by weight of the

  total charge. It has been found that the adoption of this

  is particularly advantageous for rapidly forming retro-reflective paint coatings

polymerized.

  In fact, the method according to the invention is particularly suitable for forming markings on the ground, and it. in the preferred embodiments of the invention, the polymerizable material is applied to the ground and

  vitreous microbeads carrying a catalyst are applied

  on this polymerizable material to cause in situ the polymerization and the formation of a marking on the ground. The term "ground" is used here in a broad sense and includes: roadways, sidewalks, aerodrome runways, parking areas and

  other floor coverings. According to a particular method

  simple and effective, we carry out a marking on the ground with a polymerizable paint by depositing a layer of paint on the ground and projecting into the paint

  still liquid, microbeads or a mixture of micro-

  beads containing microbeads on the surface of which is fixed the polymerization catalyst necessary to harden this paint. This process makes it possible to draw lines, drawings, letters or other signs on surfaces of concrete or tarmac for example, which are perfectly clear and visible at night in the light

  vehicle headlights. These markings can be achieved

  in a very short time and therefore with a minimum of traffic disruption. It has also been observed that the amount of catalyst required to cure. the paint was lower when this technique was used in view of the amount generally required when dispersing the powder catalyst on the paint, according to the conventional technique. In addition, the present technique makes it possible to use a simple apparatus comprising a paint spray gun and a microbead dispenser, which apparatus can be used both for marking and using polymerizable paint.

  than for marking & using traditional paints-

emulsion.

  In other preferred embodiments of the invention, a polymerizable material is mixed with the material to be incorporated as a catalyst-bearing filler and the mixture is shaped prior to its curing by polymerization. Such a method allows

  to accurately measure the amount of catalyst required

  to perform the polymerization.

  In still other preferred forms of

  According to the invention, a woven or non-woven glass fiber web carrying a catalyst is put in place and polymerizable material is then applied thereto. The fiberglass web can be deposited in a mold or on a tensioner. This is a very simple way to put

  in the form of a fiberglass-reinforced polymeric article.

  It avoids the waste of the polymer material due to the durability

  premature curing of the polymerizable / catalytic mixture

  the catalyst and can ensure a good distribution of

  on the entire surface of the fiber web of

glass.

  The invention comprises a polymer matrix formed

by a method according to the invention.

  The vitreous material bearing a catalyst is in itself a novel and useful product, and the invention extends to a vitreous material for incorporation as a filler in a polymer matrix, characterized in that a polymerization catalyst is attached. the surface of a

such matter.

  Such a product is particularly advantageous

  because it's much easier to mix

  This material is intended to be incorporated as a catalyst-carrying filler and polymerizer material than to mix a separate filler and catalyst in this material. It is therefore much easier to get a

  rapid and efficient polymerization of the polymeric material.

  The use of a vitreous charge has many advantages.

  floors; in particular, such materials are inexpensive and readily available, and they can be obtained in different shapes and sizes depending on the properties

  desired for the charged polymer product.

  Advantageously, the catalyst is adsorbed in a tackifier coating adhering to the surface of the material. This preserves and manipulates the material to serve as a filler before it is brought into contact with the polymerizable material, without loss of catalyst and without decreasing the reactivity of the catalyst vis-a-vis the material to be polymerized. As described, a number of

  materials are suitable as catalyst fixing agent

  sor. It is preferred that an organometallic compound be present as a binding agent. Many such compounds are capable of chemically bonding to the major inorganic filler materials as a monomolecular or multimolecular layer and are capable of binding the catalyst to the filler. It is especially preferred that said organometallic compound is selected from silanes, chromium complexes,

  titanium derivatives or polymers with a methoxy group

  silyl. Such compounds are particulate fixing agents

  particularly effective and they also have the advantage

  to favorably influence the coupling between the filler and the common polymeric materials,

  such as polyesters or polyacrylates.

  Different polymerization catalysts make the curing of polymerizable materials faster and / or possible at lower temperatures. The use of peroxides as a catalyst is often recommended, especially in the polymerization of unsaturated polyester resins and their copolymers. The invention comprises a material intended to be incorporated into a filler in which a peroxide, for example benzoyl peroxide (which exists in the form of a powder which is easy to

  manipulate) is surface-fixed as a catalyst.

  In certain preferred embodiments of the invention, said material to be incorporated as a filler comprises glass fibers. These fibers may be short individual fibers, or they may be long fibers constituting a woven web

or non-woven.

  14. In preferred embodiments of the invention, said material to be incorporated as a filler comprises glassy microbeads. Glass microbeads are particularly useful because their very high degree of spherical symmetry facilitates their mixing in a fluid or viscoelastic polymerizable material, so that the microbeads, and hence also the catalyst, are well distributed in its

  mass, and their use gives good listening properties.

  in any molding operation and allows a uniform distribution of the stresses inside the

formed polymer matrix.

  If it is desired to manufacture a low density article, it is possible in this case to use hollow glassy microspheres. However, if it is contemplated that good mechanical strength of the product is greater than low density, solid glass microbeads are preferred. To obtain a product with optimal mechanical properties, it may be desirable to use

  vitrocrystalline microbeads rather than micro-

  glass beads, despite their generally higher price.

  The size of the microbeads used as a filler can have a significant effect on the ease of shaping of a charged polymer matrix and / or on the possible properties of this matrix. In the case

  molded plastics, it is usually

  that the average diameter of the microbeads is

  taken between 20 and 50 microns, for example about 44 micrometers. This is related to the effect of the presence of the microbeads on the flow properties of the polymerizable material during the molding operation. On the other hand, microbeads for use in paints generally have an average diameter of between 50 and 650 micrometers, because this has been found to promote

  good reflection properties of the loaded paint.

  In preferred embodiments of the invention, the glass microbeads are selected such that their average diameter is between 20 and 650 micrometers.

  Advantageously, at least some of the micro-

  Glassy beads have rough surfaces. Such rough microbeads have larger surface areas than polished microbeads of the same size. Such rough microbeads are therefore capable of fixing more catalyst for the same average diameter and they can carry up to 3 times more catalyst than

  polished microbeads. This is particularly advantageous

  when relatively large microbeads are used and / or when rapid polymerization is necessary, and / or when such polymerization is desired at low ambient temperatures. It will be appreciated that microbeads having rough surfaces at least partially lose the reflective property for which they were initially used in road markings. This does not present a real disadvantage, because such microbeads can be mixed with uncorroded microbeads carrying the catalyst for

  to ensure the desired degree of reflecting power to the

  or other non-corroded microbeads, as well as

  as will be described below. It may actually be advantageous

  in some circumstances to use such rough microbeads to replace white pigment fillers, such as lime or carbon dioxide.

  titanium that can be quite expensive.

  In certain preferred embodiments of the invention, the material to be incorporated as a filler further comprises vitreous microbeads coated with a material which renders them both oleophobic and hydrophobic. Such a mixture is particularly well suited for use in ground marking because the microbeads carrying the catalyst can be sprinkled on the liquid paint together with the hydrophobic and oleophobic beads by means of a simple device comprising a spray gun. of paint and a 16.

  unique nozzle for the distribution of microbeads and

  lyst. The balls carrying the catalyst will sink and mix in the middle of the paint layer while

  the hydrophobic and oleophobic balls remain

  face of the paint layer where they reflect the incident light until they are eroded by the traffic and, at that time, the erosion will have revealed some of the microbeads which carried the catalyst which

  may, in turn, reflect light.

  Advantageously, the vitreous microbeads carry

  both a catalyst represent between 70% and 90% by weight of the total charge. It has been found that the adoption of this feature is particularly advantageous for rapidly forming retroreflective coatings of

polymerized paint.

  The present invention will now be described

  in more detail by means of the following examples.

* Example 1

  Microbeads are produced for introduction into road marking paint. The microbeads have a diameter of between 150 and 250u and a mean diameter. (in number of particles) of 1801u. The painting is an acrylic resin of Rohm, Plexilith

SE 663 (trademark).

  Benzoyl peroxide is dissolved in toluene

  at a rate of 200 g / l of solvent. After a few minutes

  are added, A174 (gamma-methacryloxypropyl) silane is added

  trimethoxysilane from Union Carbide). The solution containing the peroxide catalyst and the silane is poured onto the

  microbeads while the mixture is maintained in motion.

  continual After stirring for 15 minutes, the beads are dried at room temperature for 24 hours. The beads carry 0.075 gr of silane per kilogram and 8 gr of peroxide per kilogram. This mixture is stored before being

brought to the place of road marking.

  The paint is sprayed on the road and

  throw on it microbeads prepared as indicated above, at a rate of 1 part of beads per part of paint (by weight). After 15 minutes, the paint is perfectly polymerized. The retroreflective properties of the light presented by this paint are not different from those of a similar paint but in which the catalyst and bare glass microbeads were introduced separately. If one uses the technique according to the prior art in which the catalyst is supplied in separate form, it takes 2 to 3 times more

  peroxide to harden the paint in 15 minutes.

  In a variant of this example, we have replaced

  placed 20% of the beads bearing the catalyst with beads

  treated with an agent that renders them hydrophobic and oleo-

  bes such as a fluorocarbon agent of PC type 129 of 3M. The hardening of the paint takes a few minutes longer but the retroreflective properties of the paint are improved because of the presence of microbeads

  hydrophobic and oleophobic at the surface of the hardened layer.

  EXAMPLE 2 Example 1 was repeated but using a mixture of microbeads of different particle sizes. A mixture consisting of 1/3 full glass beads with a diameter of between 40 and 80B, 1/3 of balls of diameter between 75 and 1501, 1/3 of

  diameter between 150 and 250p.

  The amount of peroxide deposited on the beads was varied and silane A 174 was replaced by an equivalent amount of a grouping agent

  methoxysilyl, Polyvest 25 of H ls (trade name).

  Table 1 gives the curing time of the acrylic paint in the presence of this mixture of beads,

  for a ball / resin proportion of -1/1 by weight.

18.

Table 1

  Polyvest Peroxide Amount 25 A 174 Setting time g per kg bead g / kg g / kg 4 - 0.075 35 min. 8 - 0.075 15 min. 0.075 - 15 min.

Example 3

  Full glass microspheres with a mean diameter of 44 μ are treated with an aqueous solution of ammonium bifluoride. The beads that have undergone this treatment

  have an opaque white appearance. Their surface is rough.

  These beads are mixed with a solution of silane A174 and benzoyl peroxide in toluene. On the surface of the beads are deposited 2 gr of silane and 8 gr of

peroxide per kilo of beads.

  A methacrylic resin of the I.C.I. MDR 824 type is mixed. containing dimethyl-p-toluidine as an accelerator with 1.25 kg of microbeads per kg of resin at 20. We proceed to the shaping of the resin

  charged by injection into a mold. We observe the hardening

  molding after 50 seconds, & 70 C.

  EXAMPLE 4 Glass microspheres having a mean diameter of 44p are treated identically to those of Example 3, with a glass corrosion agent and then with a mixture of silane and peroxide. In the present example, the peroxide impregnated with the beads is peroxide

methyl ethyl ketone.

  100 parts by weight of these beads are mixed with parts by weight of Epocryl 322 acrylic resin from Shell Chemical Cy. and 0.4 parts by weight of cobalt naphthenate as an accelerator (6% cobalt). The mixture is poured into a mold at 25 ° C. The gel time of the mixture is approximately 10 minutes and the hardening is reached

after 20 minutes.

  In a variant of this example, microbeads 19. treated as above and carrying the catalyst of

  polymerization, glass microbeads with

  a coating comprising a first substance which,

  if used alone, would make the logs

  phobic while leaving them oleophilic and a second substance which, if used alone would make the beads hydrophobic and oleophobic (these beads are treated according to the process described in Belgian Patent 904.453) so as to obtain a good distribution of these

  beads in the resin and give it

  reflective summers. Said mixture is used for

to mold reflex reflectors.

  EXAMPLE 5 Solid glass microspheres about 400p in average diameter were treated with a mixture of Peroxyd-Chemie's Interox BP-40-S (Trade Mark)

  GmbH and silane A 174. The Interox BP-40-S is a suspension

  40% dibenzoyl peroxide in phthalate. This

  mixture adheres well to microbeads and is not necessary

  to dry the microbeads after treatment. Phthalate plays the role of plasticizer in the resin. In this way, 0.3 g of silane and 2.5 g of catalyst per

  kilogram of microbeads are fixed on it.

  The treated microbeads are able to be incor-

  pores in retroreflective acrylic paints.

  EXAMPLE 6 Cut glass fibers are mixed with a solution of silane A 174 and benzoyl peroxide in toluene and dried. In this way, 10 g of silane and about 100 g of peroxide per kg of fiber are deposited on

their surface.

  A methacrylic resin of the type MDR 806 of I.C.I. containing dimethyl-p-toluidine

  as an accelerator with 0.2kg of fiber per kg of

  born. The formed resin is shaped by injection into a mold. The gel time of the mixture at 20 ° C.

is less than 10 minutes.

20.

Example 7

  Glass microbeads full of about 20g of

  average diameter are treated with vinyltriethoxy

  silane A 151 (Union Carbide) and Interox BP-40-S (trademark). 0.5 g of silane and 2 g of peroxide per kg of microbeads are thus fixed on the microbeads. The microbeads are mixed with a liquid polyester resin and the mixture is immediately applied in a mold on a woven fiberglass web; we observe

  hardening & ambient temperature.

  In a variant, we do not use micro-

  beads and the catalyst is attached to the fiber surface

of glass.

Example 8

  In a variant of Example 3, solid glass microspheres have an average diameter of about 40p and they are not treated by corrosion. While mixing

  these microbeads to a silane solution A174 and peroxide

  benzoyl xylene in toluene is deposited on the surface of the beads, 0, 7gr of silane and 2gr peroxide per kilo

of balls.

  In another variant, micro

  vitrocrystalline beads of the same particle size.

Example 9

  About 25p mica of average particle size is used as a filler. By mixing the mica with vinyltriethoxysilane A 151 (Union Carbide) and

  Interox TBPB (trademark) (t-butyl perbene)

  zoate), 0.5 g of silane and 2 g of

  benzoate per kg of mica. The mica carrying the catalyst is mixed with a polyester resin of the "Bulk Molding" type.

  Compound "and is injection molded.

2 6 1 5 1 9 5

21.

Claims (19)

  A process for forming a polymer matrix filled with inorganic material, wherein the material to be incorporated as a filler is contacted with polymerizable material and a catalyst for effecting the polymerization of the polymerizable material and thereby forming the polymer matrix, characterized in that catalyst is attached to the surface of the material to be incorporated as a filler before it enters into   contact with the polymerizable material.   2. Method according to claim 1, characterized in that said catalyst is adsorbed in a coating of fixing agent adhering to the surface of the material   intended to be incorporated as a load.   3. Method according to one of claims 1 or   2, characterized in that a compound is adhered to   organometallic material to the said material intended to be incor-   porate as a charge to act as a fixer   and said organometallic compound is selected from silanes, chromium complexes,   titanium derivatives or methoxysilyl polymers.   4. Method according to one of claims 1 to 3,   characterized in that said material to be incorporated as a filler is brought into contact with a   solution containing the said catalyst and a fixing agent   in order to fix the said catalyst & the surface of the   said material, and that it is then dried.   5. Method according to one of claims 1 to 3,   characterized in that said material to be incorporated as a filler is contacted with a slurry containing said catalyst and a fixing agent to fix said catalyst on the surface of the said material.   6. Method according to one of claims 1 to 5,   characterized in that said material to be incorporated as a filler is mixed with a polyester   unsaturated to effect polymerization.   22. 7. Process according to claim 6, characterized in that a peroxide is attached to the surface of the material intended to be incorporated as filler as a catalyst.   8. Method according to one of claims 1 to 7,   characterized in that the material intended to be incorporated   as a filler comprises glassy microbeads, at least a portion of which is treated with a corrosion before being coated.   9. Method according to one of claims 1 to 8,   characterized in that said polymerizable material is applied to the ground, in that the material to be incorporated as a filler comprises glassy microspheres carrying a catalyst and in that said microbeads are applied to this polymerizable material to cause in situ the polymerization and the formation of a markings.   10. Method according to one of claims 1 to 8,   characterized in that a polymerizable material is   with the material to be incorporated as a catalyst bearing filler and that the mixture is   shaped before curing by polymerization.   11. Method according to one of claims 1 to 8, characterized in that said material intended to be incorporated as a load comprises a web of woven or non-woven glass fibers, carrying a catalyst, which is folded in place and the polymerizable material is then applied thereto.   12. Polymer charged matrix formed by a   assigned according to one of claims 1 to 11.   13. A vitreous material for incorporation as a filler in a polymer matrix, characterized in that a polymerization catalyst is fixed to the surface of such a material.   14. Material according to claim 13, characterized   in that the catalyst is adsorbed in a coating   of fixing agent adhering to the surface of the material. k615195 23.   15. Material according to one of claims 13 or   14, characterized in that an organometallic compound is present as a fixing agent and in that said organometallic compound is selected from silanes, chromium complexes, titanium derivatives or polyamines. mothers & methoxysilyl group.   16. Material according to one of claims 13 to   characterized in that a peroxide is attached to the   face of the material as a catalyst.   17. Material according to one of claims 13 to   16, characterized in that it comprises vitreous microbeads.   18. Material according to claim 17, characterized   in that said glassy microbeads have a   rough surface carrying the catalyst.   19. Material according to one of claims 13 to   16, characterized in that it comprises glass fibers.