DK152215B - STABLE, LIQUID, FABULOUS AND HARDWARE MATERIAL, PROCEDURES FOR MANUFACTURING THEREFORE AND ITS USE IN MULTI-COMPONENT MATERIALS. - Google Patents

Description

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DK 152.215 B

The invention relates to a stable, liquid, moldable and curable material of a polymerizable organic liquid and particulate inorganic fillers having improved fabrication properties, a process for preparing such materials and the use of the materials for the manufacture of composite materials which, under certain circumstances, possess favorable combinations of stiffness, strength and toughness and also may have other favorable properties such as good abrasion resistance and fire resistance. The invention relates in particular to stable, liquid, curable materials comprising a dispersion of particles of one or more inorganic substances in a polymerizable, organic, liquid precursor, a process for preparing such materials and the preparation of composite multicomponent materials upon curing thereof. said composite materials comprising an organic polymeric matrix and a particulate inorganic reinforcement phase dispersed in and bonded to said matrix.

It is known to stretch polymers by the incorporation of non-fibrous particulate fillers to make them cheaper and / or 2q to produce a stiffer product. However, simple mixing of such a filler and polymer usually produces a very weak and brittle product. More recently, it has been found that stronger composite materials can be obtained if a strong bond between the polymer matrix and the filler particles is ensured. It has now been found that by using filler particles which are finely divided and stably dispersed at high particle concentrations in a polymeric matrix by a polymeric dispersant, composite materials of great utility can be obtained which at one time may be stiffer. stronger and tougher than known composite materials. It has also been found that the use of such a dispersant in ngs agent makes it possible to produce very liquid materials with high concentrations of finely divided filler particles in polymer in serous liquids, such materials being capable of curing and directly providing said improved composite materials.

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CH patent No. 471,841 discloses a process for preparing dispersions of solid, synthetic polymer-coated particles. According to the prior art disclosed in CH Patent No. 471,841

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In two ways, the dispersions are prepared in inert organic liquids. Here it is essentially a dispersion polymerization in which generally a monomeric polymer is sieved in an organic liquid in which the monomer is soluble and the resulting polymer 5 is insoluble. This includes working in the presence of a steric stabilizer which stabilizes the fine polymer particles by separation from the organic liquid against flocculation and clumping. The essential feature by which the process known from CH patent 471,841 differs from conventional dispersion polymerisations is that the polymerization takes place in the presence of solid, possibly inorganic particles, on which a thin polymer layer is already precipitated. Under these conditions, the monomer polymerizes on the pre-formed polymer layer and forms around the solid particles a thicker coating instead of only polymer particles. However, as with a conventional dispersion polymerization, the steric stabilizer present stabilizes the particles so enclosed against flocculation. At no stage of the process known from CH patent No. 471,841 does a stable dispersion of solid particles exist in a monomer. On the contrary, the particles are dispersed in an inert organic liquid in which the monomer is dissolved. The polymerization of this dispersion / solution yields no composite material (composite) in which the solid particles are dispersed and bound in a polymer matrix. The particle size range of the particles introduced by the known process is at about 10 nm to 10 μιη. Thus, these are very fine pigment grade particles with a specific surface in the range of about 80 m2 / cm3.

From GB patent specification 1,328,136 polymeric dispersants are known which e.g. are suitable for dispersing inorganic fillers in polymerizable liquid materials. In the said GB patent, there are no indications regarding the size of the filler particles and the volume proportion of the filler. According to the only exemplary embodiment of this GB patent which shows the use of the polymeric dispersant in a polymerizable mass, 0% of 2% of a titanium dioxide pigment is used.

It is thus the object of the present invention to provide a stable, liquid, moldable and actionable material of

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polymerizable organic liquid and particulate inorganic fillers, from which the inorganic filler does not flocculate and form clumps, the material itself having a high filler amount must be liquid and suitable for the production of composite multi-component substances (multicomponent composites) with good stiffness, strength and toughness, without reducing the impact strength. This is achieved with a stable, liquid, moldable and curable material peculiar to that of claim 1. The curable material of the invention has improved manufacturing properties. From the material of the invention, composites or composite materials having a desired combination of stiffness, strength and toughness and other useful properties such as good abrasion resistance and fire resistance can be prepared. The material of the invention is hardenable to directly obtain the composite material. 15

According to the invention there is provided a stable, liquid, moldable and curable material which comprises (A) an organic liquid which can be polymerized to form a solid polymer and has a viscosity of not more than 5.0 Pa.s at the temperature at which the material should cast (B) finely divided particles, as defined below, of one or more inorganic fillers, these particles constituting at least 20% by volume of the total material, and (C) a polymeric dispersant as defined below. , and optionally a low molecular weight binder (D), as defined in more detail, wherein the filler particles are kept as a stably deflocculated dispersion in the polymerizable liquid.

By "a polymerizable organic liquid" as component (A) of the material is meant herein any one of the following groups of materials: (Al) A liquid monomer or liquid mixture of monomers which can be polymerized to form a solid polymer wherein the repeated units in the polymer chain are linked via carbon-carbon bonds or by such bonds broken by heteroatoms such as oxygen, nitrogen or silicon. The polymerization of the monomer or monomers preferably takes place without the formation of any elimination product. In other words, preferred monomers are those which polymerize by bond rearrangement reactions.

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Such reactions may be of the following types: (i) Addition polymerizations of vinyl, vinylidene or other similar unsaturated monomers in the presence of conventional free radical initiators such as peroxides or azo compounds, or 5 of conventional cationic or anionic initiators, (ii) addition polymerizations of ring-opening cyclic monomers using cationic or anionic initiators; (iii) condensation reaction type bonding reactions, if desired in the presence of conventional catalysts.

Examples of such preferred liquid monomers of type (i) include the ethylenically unsaturated monomers such as the esters of acrylic and methacrylic acids with aliphatic, alicyclic or aromatic alcohols containing from 1 to 18 carbon atoms, e.g. methylmethylacrylate, ethylmethacrylate, propylmethacrylate, butylmethacrylate, ethylacrylate, butylacrylate, 2-ethylhexylacrylate, ethylene glycol dimethacrylate, trimethylolprodylmethylene acrylate, hydroxypropylmethacrylate, hydroxyethylacrylate, dihydroxyethylacrylate those with maleic or fumaric acid derivatives such as chlorophenylmaleimide and butyl hydrogen maleate, allyl ethers and esters such as allyldiglycol dicarbonate, and other monomers of this group including acrylonitrile, methacrylonitrile, vinyl esters such as vinyl acetate, vinyl etheride, vinyl ether, vinyl ether, vinyl ether, vinyl ether

Examples of preferred liquid monomers of type (ii) include cyclic ethers, especially epoxides such as glycidyl ethers, e.g. alkyl and arylglycidyl ethers, and glycidyl esters such as "Cardura" E (registered trademark), which is the reaction product of epichlorohydrin and a mixture of branched monocarboxylic acids known as "Versatic" (registered trademark). Other examples include formulas such as trioxane, lactones and cyclic esters such as β-propiolactone, ε-caprolactone, lactams and cyclic amides such as ε-caprolactam, lauryl = lactam, pyrrolidone, cyclic siloxanes such as octamethylcyclotetra-siloxane.

Further examples of the preferred group of liquid monomers include

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are the following sets of coreactants which polymerize by reactions of the above type (iii): polyamines and polyisocyanates, polyols and polyisocyanates and polycarboxylic acids (or their aryhydrides) and polyepoxides. Suitable polyamines include ethylene diamine, hexa = 5 methylenediamine, decamethylenediamine, diethylenetriamine, piperazine, m- and p-xylylenediamine, and m- and p-phenylenediamine. Suitable polyols include ethylene glycol, diethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, tetramethylethylene glycol, neopentyl glycol, trimethylpropane, glycerol, 1,2,6-hexanetriol, 1,3- and l-cyclohexanediol 10 and p-xylylene. Suitable polyisocyanates include hexamethylene diisocyanate, 2, k- and 2,6-tolylene diisocyanate and diisocyanate diphenyl = methane. Suitable polycarboxylic acids or their anhydrides include succinic acid, adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid and 1,3- and 1,1'-cyclohexanedicarboxylic acid. Suitable polyepoxides include the glycidyl ethers of 1-butanediol, glycerol, resorcinol and bisphenol A, bis-2,3-epoxycyclopentyl ether.

(A2) A mixture of one or more preformed polymers with one or more monomers, wherein the monomeric component (s) can be polymerized to give a solid polymer product. The monomer (s) may be the same as described in (AT) above. Those undergoing a bond-rearrangement type polymerization are again preferred. The preformed polymer or preformed polymers can either be dissolved in the monomer component or be dispersed therein. The polymer can either be the same as 25 or different from the polymer formed by the polymerization of the monomer component. Where the preformed polymer is soluble in the monomer component, it can either be compatible with or incompatible with the polymer formed by the polymerization of the monomer. It may also be able to undergo grafting with the monomer.

The pre-formed polymer or pre-formed polymers can be prepared by any polymerization method, and for this purpose it does not matter whether by-products are formed during the polymerization. Thus, the polymers can be prepared by mass or solution polymerization, by suspension polymerization or by aqueous or non-aqueous dispersion polymerization, and the isolation may be by conventional methods. Where the preformed polymer is to be contained in the polymerizable liquid in the form of dispersed, colloidal particles which are insoluble in the liquid, these particles can be produced.

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may be prepared by grinding a pulp polymer to the required degree, or they may be more conveniently prepared directly using methods of aqueous or non-aqueous dispersion polymerization. Aqueous dispersion polymerization methods are described in great detail in the technical literature. Non-aqueous polymerization methods are e.g. disclosed in British Patent Nos. 9 ^ 1 * 305, 1,052.2 ^ 1, 1,122,397? 1.123.611, 1.1¾.¾) ¼ and 1.231.61¾

Finally, by using a preformed polymer which is incompatible with the polymer formed by curing the monomer component of the polymerizable liquid, a composite material in which the polymeric matrix itself is a modified composite phase, usually with a a coherent component consisting of the polymer formed during curing and a dispersed component consisting of particles of the pre-formed polymer. In this way, e.g. a glassy polymer base mass is modified by incorporating preformed rubbery polymer particles herein. Alternatively, the rubber may initially be in the form of a solution in the monomer and may be brought to phase separation as the polymerization proceeds. Alternatively, strong ionic bonding forces can be arranged on the interface 20 between the polymer phases. Such methods are well known in the context of polymer dispersion and composite substances.

Examples of mixed polymer / monomer systems suitable for use in the invention include (1) reactive polymer syrups such as (i), unsaturated polyesters, n = 25 nyl or vinylidene group terminated urethanes, hyaroxyalkylacrylic acid or methacrylic acid ester adducts of aminoplast, such as melamine formaldehyde resins, and acrylic or methacrylic acid adducts of epoxy resins, in each case in combination with and dissolved in one or more ethylenically unsaturated monomers, (ii) mixtures of polyhydroxylic polymers such as α, ω-hydroxyl polyethers, (iii) mixtures of polyepoxide-containing polymers such as epoxidized polybutadienes and novolacs or oligomeric diglycidyl ethers of epichlorohydrin and bisphenol A, with polyamines or anhydrides, (2) syrups of non-reactive polymers; those in which the polymer formed upon curing is compatible with the pre-formed polymer include poly (methyl methacrylate) / methyl methacrylate and polyamide.

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(2,6-dimethylphenylene oxide) / styrene. Those in which the two polymers are incompatible include polyisoprene / acrylonitrile, poly (butyl acrylate) / methyl methacrylate and cellulose acetate butyrate / methyl methacrylate, (3) dispersions of polymers in monomers in which they do not dissolve, such as a polybutadiene microbial cross-linked, poly (methyl meth = acrylate), in methyl methacrylate monomer, polyacrylonitrile in methyl meth = acrylate or butyl acrylate, cross-linked poly (butyl acrylate) in acrylonitrile and polyvinyl chloride in methyl methacrylate.

(A3) A partially polymerized material or prepolymer capable of fully polymerizing by any of the known polymerization mechanisms but preferably by a bond rearrangement mechanism as described under (A1) above. Such prepolymers include low molecular weight, unsaturated oligomers such as 1,2-unsaturated polybutadiene and vinyl terminated polyesters, polyepoxides such as epoxidized novolacs and polybutadiene, and prepolymers obtained by partial reaction of materials undergoing step polymerization, i.e. those which provide only high molecular weight products at high degrees of conversion of monomer to polymer. Examples of these materials are the set of coreactants mentioned above (A1), which polymerize by type 20 (iii) reactions.

The polymerizable liquid A, whether belonging to group (A1), (A2) or (A3), may be such that, upon polymerization, it forms either a crystalline polymer or an amorphous polymer, and in the latter case the polymer may be either glassy or rubbery, i.e., it may have a glass transition temperature which is either above or below ambient temperature. In the polymers there may be incorporated non-reactive plasticizers normally used in conjunction with these polymers.

To define that the polymerizable organic liquid must have a viscosity of no more than 5 Pa.s at the temperature at which the curable material of the invention is to be molded, the fact that this is the temperature at which the viscosity is molded is taken into account. has the greatest practical significance for the manufacture of composite materials from the curable material. If the viscosity at this temperature is too high, it will not be easy to mold the material. However, it is permissible for a monomer to have a viscosity at room temperature.

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temperature over the specified range if the casting is carried out at an elevated temperature as the viscosity usually decreases with increasing temperature. The temperatures at which molding and curing of the materials are carried out, respectively, will not necessarily coincide.

It is preferred that the viscosity of the polymerizable liquid is not greater than 1 Pa.s at the molding temperature, and is even better if it is not greater than 0.1 Pa.s at that temperature.

The particulate inorganic filler (B) which is stably dispersed in the polymerizable organic liquid (Å) according to the invention is characteristically a solid with a high elastic displacement modulus, namely, a modulus of at least 5 GN / m and preferably not less than 10 2 GN / m, Suitable solids may alternatively be defined as those having a Knoop hardness greater than 100. Examples of suitable solids include a wide variety of minerals such as alumina, forms of silica such as quartz, cristobalite and tridymite, kaolin and its calcining products, feldspar, kyanite, olivine, nephelin, syenite, sillimanite, zircon, wollastonite, apatite, aragonite, calcite, magnesite, barite, gypsum and other metal silicates, aluminates, aluminates , sulfa = 20 ter, carbonates, sulphides, carbides and oxides, metals which can be either brittle or tough, such as cast iron, zinc alloys, aluminum, bronze and steel, and artificially manufactured substances such as glass, porcelain, slag spoons, and carbon forms such as coke.

By stating that the inorganic filler particles are finely divided, it is believed that the particles are a maximum of 100 microns and that at least $ 95 of the number of particles has a size of 10 microns or less. Preferably over 99 $ of the number of particles has a size of 10 microns or less and it is generally such that the closer the number of such particles approaches 100 nær the better, e.g. gives a $ 30 number of 99j999 with a size of 10 microns or less very satisfactory results. It is also preferred that the maximum size of particles present should be 75 microns and the maximum size should preferably be 50 microns. The finely divided particles of the inorganic filler, which are to conform to the previous definition of particle size, are further defined herein as having a surface area of from 30 m / cur to 1 m / cm * 3, preferably from 20 m / cm * 3 to 2 3 2 m / cm * 3, determined by the BET nitrogen absorption method.

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Dead inorganic filler particles can have wide or narrow size distributions, and these can be either monomodal or polymodal at the indicated size ranges. The particle size of the filler refers to the largest dimensions of the particles. The paricles can i.

5 varying be spherical, plate-shaped, cylindrical or rod-shaped or of rectangular shape. It is preferred that the particles be of mainly granular form, as opposed to plate or rod form, since the stiffness of composite materials made from the curable materials and the fabrication of the latter for composite materials 10 are thereby best achieved. However, for special applications, particles having a length / diameter or length / thickness ratio of not more than 25: 1, e.g. certain particles of asbestos, wollastonite, silicon carbide or silicon nitride-in-whiskers, kaolin or aluminum or small mica plates.

The particulate filler may consist solely of one of the above mentioned substances, or it may consist of a mixture of two or more of such substances. The particles can be prepared by precipitation or atomization or on the basis of cohesive matter by conventional milling or rolling methods. This feature of the invention is explained in more detail below.

It is also preferred that the surfaces of the particles be at least free of loosely bound water, which can be obtained e.g. by heating the particles to 150 ° C. In some cases, e.g. when a silane interface binder is used as described below, it may be convenient to calcine the particles at temperatures above 30 ° C. It is important that the particles used are not contaminated by deliberately introduced low molecular weight surface materials, such as the fatty acids or salts thereof, with which commercially available fillers are usually treated.

As already stated, the curable materials contain at least 20 volumes of the stably dispersed particulate inorganic filler and may contain up to 90 volumes of that component. Preferred filler volume concentrations when desired to obtain the most advantageous properties of the composite materials obtained by curing the liquid materials depend to some extent on the nature of the solid polymer formed in the curing process. Where the solid polymer is amorphous and vitreous or where it is crystalline, a preferred filler concentration is from 35 volume to 85 volume 3, preferably

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from 50 volume $ to 80 volume $, based on the total amount of hardenable material. In cases where the filler particles become strongly bonded to the solid polymer, as described in detail below, such filler concentrations can result in a substantial increase not only in stiffness but also in the strength of the composite materials obtained by curing in comparison with the unmodified , solid polymer, without significant loss of toughness. When the solid polymer is rubbery and the filler particles are strongly bonded thereto, the preferred filler volume concentration ranges from $ 20 to $ 50, based on the total amount of curable material. The fracture elongation and tear strength properties of the cured materials are significantly better than those of the unmodified polymer, with only a moderate increase in stiffness. Concentrations of filler over 50 volume $ may be convenient in the case of rubbery polymers 15 for use in suspension systems, such as compression blocks for bridges or assembly blocks for machinery or as sealing caps.

The polymeric dispersant (C) used in the curable materials is * an amphipathic substance containing at least one chain-like component with a molecular weight of at least 500 solvatable by the polymerizable organic liquid (A) in the sense that if this component was an independent molecule, the polymerizable liquid would be significantly better than a theta solvent therefor; the nature of a theta solvent is described in "Polymer Handbook" (Ed.Brandrup and Immergut, Interscience, 1966) and in "Principles of Polymer Chemistry" Chapters 12-1-1 + (Flory: Cornell, 1953). The polymerizable liquid can be more simply described as being a "good" solvent for the chain-like component. The dispersant further contains one or more groups which are capable of associating with and effecting attachment to the particles of the inorganic filler (B).

Suitable polymeric dispersants can be divided into the following types, illustrative examples of which are given in the accompanying Table 1. Simple polymer or copolymer chains solvatable by the polymerizable organic liquid and terminated with a single particle attachment group. These can generally be represented as Xn Y, where X represents a monomer unit (not necessarily identical throughout the chain length), n is the degree of polymerization, and Y is a specific attachment group.

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The attachment group may e.g. may be a carboxyl, amino, sulfate, or hydroxyl group, as discussed in more detail below, and may be derived either from a suitable (co) monomer unit or from a transfer agent present to form the polymer chain. The polymer chain 5 will have a minimum molecular weight of 500, preferably its molecular weight is above 1500.

2. Irregular copolymers, solvatable by the polymerizable liquid, wherein the monomer units have a variety of particle attachment groups. These can be represented e.g. at --- XXXYYXXXXY ---, where X is a mono = 10 mer unit which gives the polymer chain solubility in the polymerizable liquid and Y is a monomer unit having a specific attachment group as in category (1). The copolymer preferably has a molecular weight in excess of 3000. The monomer units with the attachment groups are from 1 to 20 wt.%, Preferably from 1.5 to 15 wt.% And best from 2 to 10 wt. $ Of the total copolymer amount.

3 · Block copolymers which may be simple or complex: (i) Simple AB block copolymers wherein A represents a polymer or copolymer chain solvatable by the polymerizable liquid and B represents a polymer chain which is not soluble thereon manner and thereby functions as a particle attachment group. The molecular weight of the A block should be above 500, preferably above 1500, and the weight ratio of the A block to the B block is preferably between 3 * 1 and 1: 3.

(ii) Composite block copolymers, e.g. --- Am Bn Ao Bp ---, where A and B have the same meaning as in (i), and the terms m, n, o, p --- denote different lengths of polymer chain in each of the blocks. The molecular weight of each A block is preferably above 1500, and the molecular weight of each B block is preferably not less than 500. The weight ratio of. Preferably, A blocks to B blocks are as in (i).

U. Podecopolymers. These can be of three types illustrated by: (i) Am An 1 1 - ccccccc --- (ii) Am An Ao

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(iii) In the

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Bo Bp where A represents a chain solvable by the polymerizable liquid and B represents a chain which is not soluble by the liquid, the indices m, n, o, p --- denote different lengths of chains A and B, C is a monomer which gives a polymeric backbone which is (i) not soluble by the polymerizable liquid and in (ii) and (iii) can be either soluble: or insoluble by that liquid, and D is a monomer unit having a specific particle attachment group corresponding to the monomer units Y in (2) above.

In these seed copolymers, the solvable A chains have a minimum molecular weight of 500. The ratio of A chains to chains of C units in (i) or of A chains to chains of C and D units combined in ( ii) preferably between 3il and 1: 3j is best as close to 1: 1 as possible. The D monomer units in (ii) should be included in the quantities given in (2) above for the Y units. In (iii) the molecular weight of the B chains should be 15 above 500. If the chains of C units are soluble, the weight ratio of (A + C): B should be from 3: 1 to 1: 3, while the weight ratio of A :( B + C), if the chains of C units are not soluble, should be from 3: 1 to 1: 3} and the weight ratio of B: C should also be within these limits, preferably approx. 1: 1.

In choosing the polymeric dispersant to be used, it is important to avoid the amphipathic substances, especially of the aforementioned types (2) and (^ -), with solvatable polymer chains containing several groups capable of being attached to it. particulate fillers arranged so that the substances are in fact flocculants, not dispersants. Polymeric dispersants are identified as those polymers which, in their normal configuration on the interface between an inorganic particle and the polymerizable liquid, have a low concentration of attachment groups to the outer layer of polymer adsorbed on the particle, whereas the flocculants typically have a substantial or high concentration. concentration of such groups on the outside of the layer.

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Precise conditions and molecular types that achieve dispersion rather than flocculation will be well known to those skilled in the art.

It is an essential feature of the invention that the solvatable polymeric chain of the polymeric dispersant or subsequent reaction product thereof obtained by curing the liquid material must remain dissolved by or be compatible with the oligomeric or polymeric products obtained during the curing operation. , so that flocculation or aggregation of existing inorganic particles is prevented and the dispersant is deeply incorporated or bonded in the matrix of the 3 cured material. Although this requirement does not necessarily mean that any portion of the dispersant molecule must be chemically the same or similar to any pre-formed polymer or oligomer component of the polymerizable liquid (A) or even the same as or similar to the solid polymer formed upon curing, such compatibility in practice is simply obtained by selecting the dispersant such that it has a dissolved polymeric component which, in composition, is the same as or closely related to the solid final polymer. However, it can be arranged that the dissolved polymer chains of the dispersant contain functional groups, whereby grafting or copolymerization with the monomers present in the polymerizable liquid (A) can take place during the curing operation. Inoculation can be done in the case of addition polymerization of vinyl or vinylidene monomers by incorporation into the dispersant molecule of, for example, copolymerizable methacrylate groups in the manner described in British Patent Specification No. 1,052.2 ^ -1, or groups subject to hydrogen decomposition 1 presence of active radicals obtained by decomposition of a peroxide. In the case where thermosetting polymers are formed by curing the polymerizable liquid, various chemically reactive groups such as hydroxyl, amino, carboxyl, epoxy and methylol groups can be used to achieve grafting or copolymerization.

The solvatable polymeric chain of the polymeric dispersant should have such molecular weight and / or co-reactivity that, upon incorporation into the polymeric matrix after curing of the material, it has no detrimental effect on the mechanical properties of the polymer. If the molecular weight solubilizable polymeric chain near the lower limit indicated for effective stabilization is used, it is preferred that the solvatable polymeric chain being present contains some polymerizable or other reactive groups so that it can be chemically as well as physically incorporated into

16 DK 152215B

polymer foundations.

Accordingly, it will be appreciated that depending on the polymer matrix chosen is the suitability of a particular dispersant's solvatable polymeric chain.

As already stated, the particle attachment groups included in the polymeric dispersants may be of two types. The first type are those which have specific affinity for the surface of the inorganic particles and these include polar groups or chemically reactive groups which are complementary to polar or reactive groups, such as. is found on the particle surface. These can be defined in more detail as follows: (i) The groups by which a form of ionic bonding with the inorganic particle is likely to develop, e.g. carboxylic or sulfonic acid groups which can form salt-like bonds with metal ions or base-like centers in the particles, or amino or quaternary ammonium groups which can form such bonds with acidic centers in the particles; (ii) those likely to lead to the formation of a covalent bond with the particles, e.g. isocyanate or alkoxysilane groups which can react with hydroxyl centers in the particles, or chromium chloride or other chelating agents which can react with chelatable centers in the particles; (iii) those likely to lead to the formation of hydrogen bonds between the dispersant and the particle, such as carboxylic acid groups, which can react with hydroxyl groups in the particle; (iv) those whereby some physical adsorption to the particle surface may take place, e.g. through dipole-dipole reactions or van der Waal's forces; such groups include nitro, cyano, ester, amide and support groups, whose weak effects can be amplified by binding the groups sequentially to a relatively insoluble polymer chain. The other type of attachment groups are polymer chains which, in comparison with the dissolved polymer chains previously mentioned, are relatively non-dissolved by the polymerizable liquid (A), and each segment thereof has at least one, if not specific, , affinity for the inorganic particles.

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Examples of such groups are poly (acrylic acid ester) or poly (meth = acrylic acid) ester chains in which the carboxylic acid ester groups together are responsible for the attachment function, or polystyrene chains in which the aromatic rings have that function.

If desired, attachment groups of both the specified and the unspecified types mentioned above may be used.

For further illustration, some polymeric dispersants suitable for use in particular situations will be described in more detail.

Examples of dispersants which are particularly suitable for use with addition polymers derived from one or more unsaturated monomers or syrups of high molecular weight polymers dissolved in such monomers are polymers having the same molecular type as the matrix polymer having a molecular weight ranging from 20,000 to 200,000 and having a number of groups I 5 distributed along the polymer chain which are substantive to the inorganic particle. For a syrup of a 90/10 w / w copolymer of methyl methacrylate and butyl acrylate in methyl methacrylate, a suitable dispersant is a 95/5 w / w copolymer of methyl methacrylate and methacrylic acid or a metal salt of that acid. Other comonomers which are polar and substantive to inorganic materials are also useful, e.g. dimethylaminoethyl methacrylate and quaternary ions or acid salts thereof, methacrylamide, γ-methacryloxypropyltrimethoxysilane, adducts of glycidylmethacrylate with polar-substituted aromatic acids such as p

Another form of dispersant that is useful is a copolymer consisting of solvatable polymeric side chains, which are fixed at irregular intervals along a relatively insoluble polymer chain, with last chain also being irregularly attached which are capable of coating. 30 act to attach to the particles of inorganic filler. Such polymeric dispersants may e.g. are prepared by the methods described in British Patent Nos. 1,052.2 ^ 1 and 1,122,397.

Examples of dispersants particularly suitable for use with polymer matrixes obtained by polymerization, chain elongation or

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clay crosslinking of unsaturated oligomers and their solutions in unsaturated monomers are similar molecular weight oligomers containing one or more similar unsaturated groups and one or more similar polar groups. Thus, a suitable dispersant for use in a solution in styrene of an epoxy resin which has been doubly terminally reacted with methacrylic acid to form a divinyl unsaturated polymer (such materials are sold under the trade name "Derakane") is thus an oligomer which has been reacted at one end with methacrylic acid to form a terminally unsaturated form and at the other end with p-amino = 10 benzoic acid or with γ-aminopropyltrimethoxysilane to form a terminal group capable of adsorbing to an inorganic ticle surface, e.g. of silica.

Dispersants indicated as particularly suitable for one type of polymerizable liquid are not necessarily limited to use in conjunction with that type and are intended to illustrate only what is possible. Thus, the above-mentioned, terminally unsaturated dispersant can equally well be used in a simple methyl methacrylate monomer-based material.

A suitable dispersant for use in a polyurethane derived from a polyol and a polyisocyanate is obtained by grafting some of the polyol portion 20 of the polymerizable liquid onto an acrylic polymer backbone containing polar substituents. A suitable dispersant for use in an epoxy resin system can be obtained by reacting p-nitrobenzoic acid with some of the epoxy resin epoxy groups. For a system comprising a vinyl-identified urethane, a dispersant can be prepared by reacting some of the urethane through free NCO groups present therein with γ-aminopropyl trimethoxysilane.

Although in most cases the polymeric dispersant (C) will be a separately manufactured and incorporated component in the curable materials of the invention, it is not necessary that it be so, i.e. it is possible for some constituents of the polymerizable liquid (A) to act as a polymeric dispersant itself. Thus, an unsaturated polyester chain terminal carboxylic acid groups can be adsorbed on the inorganic particle surface. Monocarboxylic acid terminated chains will act as a dispersing agent, but the dicarb = 35 oxy acid chains may act as flocculants and it is preferred that these be avoided to produce a non-flocculated dispersion. Polyesters which are substantially free of such dicarboxylic acid chains,

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but containing significant amounts of monocarboxylic acid chains, can be prepared by using diol excess to produce a low acid polyester and then further reducing the acid content by reaction with a monoepoxide such as e.g. disclosed in British Patent Specifications Nos. 1.0 ^ -5,199 and 1,317 * 605. It is also possible to form the dispersant in situ while the filler is dispersed in the polymerizable liquid, e.g. due to the existence of a low molecular weight substance already containing a potential filler attachment group which can combine with a dissolved polymer chain. Epoxide-containing 0 soluble polymer chains can e.g. combine with the carboxyl group in a nitrobenzoic acid during the dispersion step.

The amount of polymeric dispersant (C) used in the materials of the invention is subject to great variation, depending on the nature of the linking groups in the dispersant, the particulate inorganic material selected, particle surface area and concentration, and the nature of the polymerizable liquid, but In general, a satisfactory minimum fraction of 0.01 g / m of the total particle surface area is determined by the BET nitrogen absorption method. An appropriate minimum amount of polymeric dispersant is important to ensure that the inorganic particles do not accumulate in the curable material and thus remain during the curing of the material. Generally, higher concentrations of polymeric dispersant are required when the inorganic particle concentration and the total surface area are high, and also when the polymerizable liquid contains a soluble, preformed oligomer or polymer. Above a certain optimum level, no additional particle stability benefits are obtained by increasing the amount of polymeric dispersant.

When the curable materials of the invention comprise two or more types of finely divided particulate material or when, in addition to the particulate inorganic filler, a pigment as mentioned below is included, it may be convenient to use two or more different polymers dispersants. In these dispersants, the attachment or "anchor" components may be selected differently, taking into account the surface properties of the particles in question. The solvatable polymer chains in the dispersants may be either Identical or Different, but if different, they must nonetheless be compatible with one another and with other components of the curable material as previously described.

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While not important for achieving some of the advantages of the invention, it is preferred that the curable materials of the invention, in addition to the polymerizable organic liquid (A), the particulate, inorganic filler (B) and the polymeric dispersant (C), are preferred. 5 already described also contains a low molecular weight binder (D) which provides active groups, thereby ensuring that the polynesial groundnose and the particles bond very strongly in the final composite material obtained after curing. Some degree of bonding between the matrix and the particles always exists, simply because of the presence of the polymeric dispersant, whose properties result in being placed on the interface between these two phases and exhibiting an affinity for both of them. However, in order to obtain composite materials with the best possible mechanical properties, it is necessary that the strength of the bond between the polymeric matrix and the particles is at least as great as the internal cohesive strength of either of the two constituents which may be weakest.

In suitable cases, the required strong bonding can be achieved by the use of a suitably selected polymeric dispersant, whereby the forces connecting the dispersant to the particles are sufficiently strong and the solvatable polymeric chain of the dispersant is fully integrated into the polymeric matrix after curing. , either by chemical reaction or by being a compatible polymer of similar molecular weight.

However, the preparation of a very strong bond between the polymeric base mass and the particles is preferably achieved or promoted by including in the curable material a low molecular weight binder of the type containing one or more groups capable of reacting. with groups of the inorganic material, and also one or more groups which can copolymerize with or otherwise be deposited on the polymer which constitutes the matrix of the final composite material. In the use of a low molecular weight binder of this type, it must be ensured that the binder, like the polymeric dispersant, is on the interface between the two forms to be bonded. This requires that the amounts of dispersant and bonding agent used must be adjusted so that nothing particular achieves saturated coverage of the particle surface and thus leaves no room for the other agent to be adsorbed.

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The particular type of binder to be used will depend on the nature of the inorganic filler and the polymerizable organic liquid. Suitable bonding agents are generally substances which contain groups which can form a variety of ionic, covalent or hydrogen bonds with the particle, and also groups which can react to form bonds with the polymeric matrix. Suitable groups for bonding to particles with hydroxyl, metal oxide or silica surfaces are e.g. the oligomeric hydrolysis products of alkoxy silanes, chlorosilanes and alkyl titanates as well as the trivalent chromium complexes of organic acids. When the particle surface has a basic character, e.g. in the case of particles of alkaline earth metal carbonates or metals such as aluminum, chromium and steel, suitable bonding groups are carboxylic acid groups. In the case of particles with acidic surfaces, such as those of kaolin, amine salt groups are suitable for bonding to the particles.

Typically, groups suitable for bonding with the polymeric matrix are those which react with the polymerizable liquid during the polymerization step. Thus, an interface binding agent containing an ethylenically unsaturated group is suitable for use in connection with addition polymerization systems which include vinyl, vinylidene and the like unsaturated monomers. An agent containing an amino, an oxirane or a carboxyl group is suitable for use with epoxy group-containing compounds. Examples of suitable interfacial bonding agents include: γ-methacryloxypropyltrimethoxysilane 25 γ-aminopropyl trimethoxysilane γ-glycidyloxypropyl trimethoxysilane vinyl triethoxysilane vinyl triacetoxysilane vinyl trichlorosilane 30 acrylic and methacrylic acids and their metal salts methacrylato maleimidopropionic succinimidpropionsyre 35 H-aminomethylpiperidine and tetraisopropyl tetrabutyltitanater.

Generally, such amounts of the interface bonding agent as are customary for polymeric materials are used.

22 DK 152215 B

with inorganic fillers. A suitable minimum quantity for most 2 applications is ea. 0.001 g of binder per m filler particle surface area. If desired, a mixture of two or more interface binding agents of the types described can be used.

Cured materials of the invention may contain dyes or pigments. These constituents may be dissolved or dispersed in the complete mixture of the polymerizable liquid, the finely divided, inorganic filler and polymeric dispersant, or in the case of pigments, they may be added to said mixture as a pre-formed dispersion in the polymerizable liquid. liquid which has been prepared by a suitable pigment dispersant, e.g. a dispersant of the type disclosed in British Patent Specification No. 1,108,261 or in German Publication No. 2218613.

The curable materials may also incorporate coarse granular "filler" particles or coarse fibrous material which is dispersed but not stably dispersed in the other constituents. By "coarse" is meant herein that the average diameter of the grains or fiber yarns is at least 10 times greater than the average diameter of the finely divided inorganic filler particles, as previously defined. Under these conditions, the finely dispersed particles of the stable dispersion behave essentially as a liquid against the coarser particles, i.e., contrary to their skill and to move the coarser particles through the dispersion is the same as it would be through a pure liquid of similar viscosity and density. In the composite materials obtained by subsequent curing, the polymer formed together with the finely divided particles is substantially a binder with good mechanical properties for the coarse particulate material. Because there is no interaction between the coarse and the finely divided particles, it is not necessary to modify the amount of the latter particles in proportion to the amount of the polymerizable organic liquid relative to that which would itself without the presence of the coarse material.

The application also relates to a process for producing stable, liquid, moldable and curable materials as previously defined, which process is characterized by dispersing the finely divided filler (B) in the component (A) in the presence of the dispersant (C). and optionally the binder (D) such that the filler (B) represents at least 20% by volume of the total material that in a

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organic liquid (A) which can be polymerized to form a solid polymer and having a viscosity not greater than 5.0 Pa.s at the temperature at which the material is to be cast, finely divided particles (B) are dispersed as before. defined by an inorganic filler 5 in the presence of a polymeric dispersant (C), as previously defined, such that the filler particles make up not less than 20 volume o / o of the total material.

The polymerizable organic liquids, the inorganic fillers and the 10 polymeric dispersants suitable for use in this process are those described above. It is to be understood that the polymerizable liquid may optionally contain a certain amount of pre-formed polymer which may be either identical to or different from the polymer formed by curing the polymerizable liquid 15 itself. It is also to be understood that, in addition to the polymeric dispersant, an interface binder may be included as described above. The process of dispersing the particles of the inorganic filler in the polymerizable liquid can be carried out by any of the methods commonly used in the paint industry to produce dispersions of pigments in liquid carriers, if desired at a temperature above room temperature. Thus, where the filler is already available in the required primary particle size, the process may conveniently be a method for dispersing the particles in the polymerizable liquid using methods such as ball milling, combined milling and kneading, or other methods by which the dispersion is displaced, and the aggregation. of the particles thereby dispersed and distributed by the liquid. Alternatively, the comminuted particles can be prepared directly in the presence of the polymerizable liquid or in a liquid component thereof and also in the presence of the polymeric dispersant by comminution (decomposition) of coarse, non-colloidal particles. In such a process, easily accessible raw materials such as coarse sand used in glass making can be exploited, the difficulties and dangers of handling fine powder (e.g. explosion or health hazards such as risk of silicosis) 35 avoided and the extent of drying, which necessarily follows the normal preparation methods in an aqueous medium is reduced. In addition, it has surprisingly been found that the composite materials obtained by curing liquid materials prepared by this particular method, wherein a low molecular weight binding agent of the aforementioned

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The 24 types also included in the comminution operation have better properties than those produced from liquid materials containing the same inorganic filler particles prepared by prior grinding in aqueous media and then drying normally at 100 ° C. It is believed that these benefits can be attributed to (1) the relatively low initial amounts of chemisorbed water introduced by the use of coarse, inorganic particles, (2) the reduced probability of contamination of newly formed particle surfaces with water or other small molecules, and the increased opportunity for strong adsorption of the polymeric dispersant on those surfaces and, if present, the interface bonding agent. However, if desired, comminution of the inorganic filler material can be carried out in a suitable non-aqueous liquid other than the polymerizable liquid, after which the liquid is removed by drying and the particles subsequently redispersed in the polymerizable liquid.

15

Comminution of coarse material in the size range of 100 to a few thousand microns to produce smaller particles is readily accomplished by using conventional ball mills, rotary ball mills (attitors) or vibration mills with preferably spherical or cylindrical grinding media which are harder and denser than filler material, using ratios of the size of the grinding media to the average starting particle size of approx. 10: 1 or up to 100: 1, where the polymerizable liquid is highly viscous. Multistage treatment with media of different dimensions or the use of mixtures of media of varying size and shape may be necessary to obtain very fine particle sizes or special particle size distributions.

Where the curable materials must contain an interface bonding agent, this can be introduced either during or after the process of redistributing the inorganic particles in the polymerizable liquid or their preparation by comminution, as the case may be. The binder may simply be mixed in the dispersion, but it is somehow preferred to ensure that the binder is joined to the inorganic particles. Where the binder e.g. is a silane derivative, as mentioned earlier, it will be advantageous to ensure that sufficient water is present in the system or that sufficient water is added to the system to allow an almost complete

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25 of the silane derivative. This can be promoted by heating and the addition of a suitable catalyst such as n-alkylamine or a dialkyltin dicarboxylate.

Cured materials of the invention have excellent storage stability. Any precipitate is easily dispersed. In cases where it is desired to prevent precipitation, this can be achieved by the addition of bentonite clay, roasted silica, hydrogenated castor oil or other materials well known in the paint and colloid fields.

10

The application also relates to the use of the material according to the invention in multi-component materials.

As already mentioned, it is advantageous that the curable materials contain large volumes of the finely divided particulate inorganic filler and yet retain a very low viscosity. In materials containing 50 and 55% by volume of finely divided granular particles, e.g. relative viscosities of only 10 times and 100 times the viscosity of the polymerizable 2o liquid are obtained, respectively. Such relative viscosities greatly approach the minimum achievable for non-aggregated, monodispersed spheres (cf. JS Chong, EB Christensen, and AD Baer, J. Applied polym. Sci. Vol. 15, 2007-2021 (1971) )).

Thus, for a monomer such as methyl methacrylate having a viscosity of 0.5 mPa.s, filled dispersion viscosities of 5 mPa.s for 50% by volume and 50 mPa.s for 55 volume ^ have been obtained. In the case of a resin / rhinomer system having a viscosity of 0.5 Pa.s, filled dispersion viscosities of only 5 and 50 Pa.s for 30% and 55% by volume, respectively, are possible.

A further feature of the invention is the fact that the viscosity of the materials is very low even at very low shear rates, i.e., the materials have Newtonian or nearly Newtonian character at low shear rates and have not aggregated or

26 DK 152215 B

flocculated filler-induced thixotropy (however, the materials may be somewhat thixotropic where an anti-precipitant such as bentonite as mentioned above has been added or where the polymeric liquid itself has thixotropic character). Also, due to the fine particle size, there is little tendency to settle in the low viscous media during the casting and curing process, and there is no tendency for harmful cavity formation when the materials are displaced, which frequently leads to cavity formation with coarse slurries.

For most of the possible methods of making curable materials, it is preferred that the material has a viscosity of not more than 100 Pa.s. under the temperature and shear conditions whereby the material must be molded. However, for some applications viscosities above this limit may be acceptable. Where, on the other hand, low pressure molding methods are to be used, it may be convenient that the viscosity of the material does not exceed 10 Pa.s. and the amount of polymeric dispersant used in such a way as to obtain a curable material of acceptable viscosity in connection with a given fabrication method will generally be readily obtainable by those skilled in the art.

These features enable the preparation of articles of the curable materials by methods which cannot be used in connection with the previously known materials containing fine particulate filler due to their high and often non-ideal viscosity.

Furthermore, the presence of the large amount of inorganic material facilitates the casting of large objects directly from the curable liquid materials at atmospheric pressure or pressure slightly above this.

The heat of polymerization formed by the polymerizable liquid during curing is absorbed and dissipated by the filler material. This factor significantly reduces the chance of void formation by boiling the monomer and in cases where sufficient inorganic filler is included, the chance of void formation can be completely eliminated since the rise in temperature during polymerization will not exceed the boiling temperature of the monomer. heat lost to the mold in a relationship which occurs in practice with thick section moldings. In those cases where the material's "heat sink"

27 DK 152215B

however, the site is not sufficient to prevent boiling; eg. when a rapid polymerization is initiated at a temperature close to the boiling point of the monomer, cavity formation can be prevented by causing early gelatinization of the material by introducing a crosslinking reaction in the curing process. In the case of a material based on addition polymers, this can be achieved by the presence of polyfunctional forms which form part of the polymerizable liquid such as ethylene = glycol dimethacrylate, the polymerizable liquid being mainly based on methyl methacrylate. Alternatively, a separate gelatinization reaction can be produced, such as the reaction of a polyisocyanate with oligomers containing a wide variety of hydroxyl groups present in the polymerizable liquid, after which the curing is complete by a free radical-initiated addition polymerization.

Curing of the materials of the invention may be accomplished if desired using closed molds at atmospheric pressure, and rapid curing in the absence of any crosslinking reaction is then possible without boiling the monomer, but this requires expensive equipment and is not appropriate in connection with very large casts.

A variety of methods can be used to make articles from the curable materials of the invention. They can be molded by simply molding the mixture into molds and initiating the polymerization. Sheets, rods, beams and other suitable shapes can thus be easily obtained. The initiation can be induced by heat-activated catalysts or by the addition of catalysts immediately before casting, where cure at room temperature or lower temperatures is required. A preferred modification of the simple molding technique is to inject the curable, liquid material under low pressure into closed, corresponding forms. For this process, pressures of less than 0.69 bar are required and thus cheap lightweight molds can be used, and casts of very large surface areas are practically feasible, while higher pressures are usually required for conventional filler-containing materials. A further variation of this technique is to fill the mold with fiber threads before injecting the dispersion into the mold so that it penetrates through the fiber network ("resinjection"). Again, low pressures are required and 35 casts with large surface areas can be made. Although the injection of reactive resins into sealed molds filled with filamentous wires is known together with the associated advantages, e.g. avoiding the difficulties of casting fiber / resin dispersions,

28 DK 152215 B

when better reproducibility than is possible with manual feeding, and the manufacture of two good surfaces with the possibility of casting with ribs and ribs, it has not previously been practically possible as a method of use in conjunction with materials with 5 high solids content. The filler-containing materials known prior to the present invention would either have an excessively high viscosity or contain coarse or coalesced particles filtered by the fibrous web. Both of these effects provide a high back pressure which prevents the mold from being filled. However, many of the materials of the invention are very low viscous and also contain finely divided non-aggregated particles. They are therefore able to pass through and soak the fibrous tissue.

The fibers for use in this process can be either organic textile fibers or inorganic fibers of e.g. glass or metal or a mixture thereof. They may most conveniently be introduced into the mold in the form of a mat, although loosely cut threads and sprayed preforms coupled with a small amount of resin may also be used. In general, the fibrous material should contain a large amount of pores 5 times larger, preferably 10 times larger in diameter, than the average size of the filler particles. This is most easily achieved for fiber volumes up to K0 0 using fiber materials made of fiber yarns of thicknesses of at least 5 times, preferably at least 10 times the filler particle drying. Suitable fiber materials of this type are commercially available. In the case of glass fibers, these are available as multifibrillar filaments containing from 20 to 1000 10 microns of fibrils per second. thread or string. Materials made of fibers having a diameter equal to or smaller than that of the particles can be used, but only at lower fiber volumes.

Composite materials containing fibers can also be prepared by conventional methods, such as by hand and press molding, from blends of the curable materials and cut fiber blends. Here, the low viscosity can again be an advantage, resulting in low molding pressures and easier wetting and degassing.

Composite, layered castings can be advantageously prepared by the injection technique. Thus, a core material can be completely encapsulated, such as e.g. may be a low density foam and its combination with a coating of the high modulus and high strength composite materials of the invention provides light, very rigid and

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29 strong structures. The core is placed in the mold which is then closed and the curable liquid material is injected around it. Along with the core, fiber mats can also be placed in the mold. These serve to place the core of the mold and then make the finished casting surface 5 tough.

Core encapsulation can also be accomplished by distributing the liquid material on each side of the core before placing it in a mold and then closing the mold so that excess liquid is pressed out. Fiber mats can also be placed on either side before being placed in the mold.

Another type of layered casting is that in which the materials of this invention are bonded during the curing operation to one side of a preformed molded sheet or shell. A molded shell must be vacuum thermoformed e.g. of a plastic sheet, a corresponding mold is placed behind it to form a closed cavity, the curable material is injected into the cavity and then cured. In this way, a composite article is obtained in which the cured composite material according to the invention is attached to one side of the plastic. In this way, thin plastic molds can be made and reinforced while combining the simplicity of vacuum forming thermoplastic materials with the convenience and ease of low pressure injection of the materials of the invention.

The curable materials of the invention can also be rotationally molded to obtain complex hollow shapes and tubes. The liquid material is placed in a mold and the mold is rotated about one or more axes, depending on the complexity of the article as the curing is performed. Due to the absence of boiling monomer, the easy removal of air and the good flow properties of the liquid material, 30 large, flawless castings can easily be made. Optionally, fibers may be introduced into the molding.

The cured moldings described above can be further processed and adhered if desired. It has also surprisingly been found that the cured composite materials of the invention can be thermoformed and can be extended to a great extent without fracture at a temperature above the glass transition temperature of the polymer matrix, where

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it is amorphous, or above its melting point where it is crystalline. Thus, heated sheets can be shaped by the influence of positive or negative pressures to introduce it into a mold. Conventional composite materials containing coarse, poorly attached or aggregated particulate fillers are usually bleached and subjected to fractures by small deformations and cannot normally be thermoformed in this way.

In all of the above fabrication processes, it is advantageous to use internal or external release agents to prevent adhesion of the 10 cured composite materials to the mold and to obtain a good finish. This is well known in the art. Examples of internal release agents are alkali or alkaline earth metal alts of fatty acids and alkyl phosphates and their neutralized derivatives. Suitable external release agents include poly (tetrafluoroethylene), silicone and polyvinyl alcohol-1 coating on the molds.

Multicomponent compounded materials made from the material of the invention, in which the polymer matrix and the inorganic particles are firmly attached to each other, provide an unexpected and valuable combination of mechanical and physical properties, in so far (contrary to accepted practice) not only the rigidity , the strength also continues to grow as the concentration of the inorganic particulate phase is increased all the way up to the previously stated maximum concentrations. The impact strength of the polymer matrix is also greatly retained and increased in some cases. The cured composite materials have very good abrasion resistance if high Moh hardness particles such as quartz and alumina are used. They are also significantly more fireproof than polymers without filler, and even when burned, their contribution to the overall amount of fire is low and the flame size and propagation rate are low. Materials having particularly good combustion resistance can be obtained by using finely divided fillers containing completely or partially hydrated water which is released by heating, e.g. alumina trihydrate and calcium sulfate hemihydrate.

Products where the composite materials contain coarse fibers, as previously described, are made significantly tougher. The use of a coarse, 35 granular constituent makes it possible to produce a composite product having an inorganic content greater than 95 i / w which, although having a lower strength than the modified polymer matrix, is significant

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stronger and more durable than a conventional hydraulic cement.

It is clear from the mechanical properties and potential fabrication processes described above that the composite materials of the invention are suitable for a wide variety of applications.

5 Objects that benefit from the good finished surface, abrasion resistance, light pigmentation, and fire resistance attainable include work surfaces, decorative wall coverings, furniture parts, sometimes tables and sanitary ware. Articles which utilize the high stiffness and strength of the materials and the possibility of fabricating large, thin-bellied casts in the "resinjection" process are e.g. car parts, bathtubs, boats and furniture shells. Objects which can be manufactured by rotational molding include pipes, silos, vehicles, toys and storage tanks.

The invention is illustrated by the following examples, in which parts and percentages are parts by weight and percentages, unless otherwise stated.

The hardenable materials, unless otherwise stated, are cast as approx. 5 mm thick sheets. Products with bending modulus and strength are determined at 25 ° C for three-point bending, the beam length being 10.16 cm and the bending rate 5 mm / minute. The impact strengths are all determined 20 at 25 ° C using that in B.S. 2782: Part 3, Method 306D (1970) described Charpy Impact Testing Machine. The abrasion resistance is determined by a Taber Abrader apparatus (Taber Instrument Corporation), using CS10 slices and a 1000 g load for 1000 periods in each trial. The sample is weighed before and after the test, 25 and the weight loss per 1000 periods is recorded. The particle size distributions are determined by well-known Coulter counting methods.

Example 1

This example illustrates the preparation of a liquid, curable material of methyl methacrylate and quartz silica, using as an polymeric dispersant an acrylic copolymer in which quaternary ammonium groups effect attachment to the surface of the particles.

A finely divided, dry milled and air sorted quartz silica (Minusil 5, ex Pensylvania Glass Sand Corporation) with a surface area determined p by nitrogen absorption of 5.0 m / g and a particle size distribution 35 as follows:

32 DK 152215 B

Particles of 10 microns or less 99) $ 999 by number (97) 5% by weight) Particles of 50 microns or less - (100.0% by weight) are dispersed in methyl methacrylate (containing 100 parts per million "Topanol" A * inhibitor) in the presence of 1.7 weight calculated on silica = 5 ca of a copolymer dispersant (methyl methacrylate 81, 6 parts, ethyl acrylate 9) 6 parts, dimethylaminoethyl methacrylate ^ 8 parts, quaternized with benzyl chloride +, 2 parts) with Mw determined by gel permeate -tion chromatography (GPC) 20,000 and in the presence also of 1.8% by weight, based on the silica, γ-methacryloxypropyltrimethoxysilane to produce a very liquid, non-flocculated dispersion (Ford Cup No. k viscosity at 20 C less than 15 seconds). The dispersion contains 67 weight $ silica.

100 parts by weight of this dispersion is heated to 100 ° C and then cooled to room temperature. 0.6 parts by weight of "Perkadox" Yl6 ** is added (2 weight $ 15 calculated on the monomer). The initiated dispersion is cast in a flat plate mold lined with ”Melinexn film and heated for 2 hours to 50 ° C and 2 hours to 80 ° C. The finished cast is very glossy and flawless, contains 50 volume $ silica and has a bending modulus of 12.6 GN -2 -2 m, bending strength of 110 MN m, and Charpy impact strength without notch of 6.0 20 KJ nf2.

* "Topanol" A is a registered trademark of Imperial Chemical Industries Limited for 2, in + -dimethyl-6-tert. -butylphenol.

** "Perkadox" Yl6 is a registered trademark of AKZO-Novadel for bis ((tert -butylcyclohexyl) peroxydicarbonate.

25 *** Mtøe] _j_nexi! is a registered trademark of Imperial Chemical

Industries Limited for a biaxially oriented poly (ethylene = terephthalate) plate.

Example 2

Example 1 is repeated, but with an increased concentration of silica. Thus, using the same constituents as before, but less methyl meth = acrylate, a 69 wt.% Dispersion is produced which has a Ford No. cup viscosity at 20 ° C in 19 seconds. It was cured as described in Example 1 to give a flawless, glossy sheet with a silica volume of -2 52.5 $), a bending modulus of 12, GN m, and a bending strength of 110 MN 35 m.

33 DK 152215B

Example 3

Example 2 is repeated but the silane derivative is omitted. A liquid dispersion is obtained with a Ford No. 4 cup viscosity at 20 ° C in 16 seconds.

Yed curing as described in Example 1 yields a flawless, glossy 5 sheet with a silica volume of $ 52.5 which is somewhat weaker and brittle than the one obtained in Example 2.

Example 4 In this example, the polymeric dispersant of Examples 1-3 is replaced with another acrylic copolymer, wherein carboxylic acid groups are included to provide attachment to the silica particles.

Example 1 is repeated except that the dispersant used in this example is replaced by 3) 4 parts by weight, based on the amount of silica, of a copolymer dispersant (methyl methacrylate 98 parts, meth = acrylic acid 2 parts) with M (G.P.C.) 110,000. A liquid dispersant is obtained.

W

15 sion. The finished cast is glossy and flawless and has a bending 2 modulus of 10.4 GN m, a bending strength of 127 MN m ~ and a Charpy impact 2 strength of 6.5 KJ m.

Comparative Examples Å-F

To illustrate the importance of incorporating a polymeric dispersant, experiments with the preparation of a variety of materials using the same quartz silica at the same concentration as before, either under complete omission of the polymeric dispersant or substituting it with a conventional dispersant.

Comparative Example A

Quartz silica as described in Example 1 (67 parts by weight) is displaced into 33% by weight methyl methacrylate. A powder cake is obtained without any fluidity.

Comparative Example B

Quartz silica as described in Example 1 ($ 67 wt) is displaced in an intermediate

34 DK 152215 B

addition of 31.2% by weight of methyl methacrylate and 1.1½% by weight of Y-methacryloxy prop = pyltrimethoxysilane (1.7% by weight on silica). A very thick, flocculated mixture is available which cannot be molded. It is pressed into a mold and cured as described in Example 1 to produce a cracked 5 plate with defects.

Comparative Example C

Quartz silica as described in Example 1 (67% by weight) is displaced in a mixture of 30 parts of methyl methacrylate, 1.1½% by weight of γ-methacryloxypropyltri = methoxysilane and 1.2% by weight sodium stearate. A thick, flocculated, non-molded mixture is formed which, after pressing into a mold and curing as described in Example 1, gives a cracked cast with failure.

Comparative Example D

Comparative Example C is repeated, but the sodium stearate is replaced with a nonylphenol / ethylene oxide condensate.

As a result, a flocculated mixture and a cracked cast with errors are obtained.

Comparative Example E

Comparative Example C is repeated, but the sodium stearate is replaced with c ethylpyridinium b romide.

The result will be a flocculated mixture and a cracked cast with failure.

Comparative Example F

To illustrate the improved mechanical properties of the filler-containing materials described in Examples 1 - +, in comparison with the properties of the polymer matrix, the methyl methacrylate used in Example 1 is polymerized under the same conditions described in this Example. . The polymer obtained has a bending modulus of 350 GR m, a bending strength of 10Q MR m and a impact strength of 6-8 KJ m

DK 152215B

Examples 5-11 In this series of examples, dispersions of comminuted α-quartz silica are prepared by comminution (crushing) of coarse silica glass sand in the monomer.

Example 5 5 312 g of coarse quartz sand for glass fabrication (Harrison Meyer W + 31), of which 80-86 wt., Has a particle size ranging from 150 to ^ 20 microns, 133 g of methyl methacrylate, 0.5 to 5 g (0.15 weight <fo calculated on silica] γ-methylacryloxypropyltrimethoxysilane and 2.8 g copolymer dispersion

(98: 2 methyl methacrylate / methacrylic acid copolymer with M

w 10 110,000 (G.P.C,)) is transferred together with 1,050 g of 9 mm steatite balls to a 9 liter ball mill. The ratio of the amount added to the cavities between the balls is 1: 1. The mill is rotated at 60 rpm for 2k hours. After separating the beads, a dispersion consisting of 73 wt; $ finely divided quartz silica is obtained from the monomer having a Ford cup No. 4 viscosity of 58 seconds at 20 ° C and a viscosity of 0.04 Pa.s at a shear rate of 20 seconds ”· *” and 25 ° C. The particle size distribution of the thus obtained quartz is as follows:

Particles of 10 microns or less 99? 7 $ calculated on number (55.0 wt fo) Particles of 50 microns or less - (100.0 wt $) p 20 The surface area of the sand after comminution is approx. 2 m / g. The surface area 2 before the comminution is less than 0.10 m / g.

To 17357 g of the above dispersion are added 15? 3 g of methyl meth = acrylate and 1.18 g of "Perkadox" Yl6 initiator (2% by weight based on total monomer content). The dispersion is then cast and cured as described in Example 1. A glossy, flawless plate containing 67% by weight (50 volume ^) of silica is obtained. The mechanical properties thereof are given in Table I.

Example 6

The comminution treatment described in Example 5 is repeated, but the silane derivative is omitted. A liquid dispersion of 73 wt. Colloidal fine silica in methyl methacrylate having a similar viscosity and particle size distribution as obtained in Example 5. is obtained. To 173

_l I

36 DK 152215B

15.3 g of methyl methacrylate and 1.8 g of "Perkadox" Yl6 initiator are added. The dispersion is then cast and cured as described in Example 1. A glossy, flawless plate containing 67% by weight (50% by volume) of silica is obtained and the mechanical properties thereof are given in Table I.

Comparative Example G

The comminution described in Example 6 is repeated, but the copolymer stabilizer is omitted. A flocculated mixture is obtained which cannot be separated from the steatite grinding medium.

Example 7 To 173.7 g of the dispersion prepared as described in Example 6 is added 15.3 g of methyl methacrylate, 1.18 g of "Perkadox" Yl6 initiator and 0.19 g of γ-methacryloxypropyl trimethoxysilane (0.15% dry weight based on silica The dispersion is allowed to stand for 2k hours, then cast and cured as described in Example 1 to produce a glossy, 15 flawless plate containing 50% by volume of silica and with mechanical properties as set forth in Table I.

Example 8

Example 7 is repeated except that the dispersion is heated in the presence of the silane derivative to 100 ° C for 5 minutes and then cooled to room temperature before initiator addition and curing. A glossy, flawless plate containing 50% by volume of silica and with mechanical properties is given in Table I.

Example 9

Example 7 is repeated but with 0.050 g of n-propylamine added. The mechanical properties of the cured product are listed in Table I.

Example 10 I.56O g of the coarse silica sand described in Example 5? 600 g of distilled water and 1.2 g of sodium hydroxide are transferred to a 4.5 liter ball mill together with 5,300 g of 9 mm steatite balls. The ball mill is rotated for 2 hours as in Example 5, and after separation of the balls from the batch, a liquid dispersion of fine silica sand is obtained in water. silica sand

37 DK 152215B

has, after comminution, a particle size similar to that of Example 5. The dispersion is then treated with 0.15% by weight of Y-methacryl = oxypropyltrimethoxysilane sand as a 5 µl solution in water whose pH has been adjusted to 3.5 with acetic acid. The dispersion is air-dried overnight and then dried in an oven at 185 ° C for 2 hours. To 312 g of the thus obtained dry silane-treated silica are added 1 * + 9 g of methyl methacrylate monomer and 2.8 g of the copolymer dispersant described in Example 5 · The dispersion is sheared for 1 hour to disperse the particles and a liquid is obtained. , stable dispersion. The dispersion is then initiated, cast and cured as described in Example 1 to produce a flawless plate containing 50 volumes of silica and having mechanical properties as set forth in Table I.

Example 11

Example 5 is repeated, but using 9 t, 9 g of Y-aminopropyl tri = 15 methoxysilane instead of the γ-methacryloxypropyl trimethoxysilane.

Table I

Bending Bending Charpy Module Strength Strength,

Material type GN m- ^ MN m ~ 2 KJ m-2

Ex. 5 Silver derivative added 12.5 1¾¾ 6.8 20 before comminution

Ex. 6 No silane derivative 12.0 60¾ 2.5

Ex. 7 Silver derivative added 12.0 78-5 3.9 after comminution

Ex. 8 Silane derivative added 13) 0 120¾ 6¾ 25 after comminution with subsequent heating

Ex. 9 Silane derivative added 13) 0 120-9 6.3 after comminution with 30 n-propylamine catalyst

Ex. 10 Sand find el t in water 12.0 73¾ 3) 7 treated with silane derivative, dried, then redispersed in monomer

Ex. 11 Another silane derivative 13) 0b 1.8 used than that of Examples 5-10

_1 I

38 DK 152215B

Table I (continued) Bending Bending Charpy Module Strength Strength

Material type GN m ~ 2 MN mi KJ

5 Comparison Ex. Polymer Primer 3 100 6-8 F See Without Filler In the above table, the results of Example 5 illustrate the effectiveness of adding the interface binder during the comminution step with the polymeric dispersant as compared to simply adding it after the comminution (Example 7) or pre-treating it. aqueous finely divided silica (Example 10). Examples 8 and 9 illustrate the advantages of heat and catalyst treatment to promote utilization of the interface binder. The relatively poor properties of the product of Example 11 illustrate the importance of choosing an interface binder which can react with the polymer backbone. Example 6 shows that omission of added binder leads to a similar result.

Comparative Examples H-I

These two examples illustrate the importance of using finely divided particles of the inorganic filler.

Comparative Example H

The coarse silica sand (average particle size 250 microns) of Example 5 is mixed with the methyl methacrylate, silane derivative and polymer = 25 stabilizer described in the example of a slurry containing 67 weight silica which is precipitated too quickly to cast . To obtain a sample for comparison, the sand is slurried in a syrup of 7.8 parts of poly (methyl methacrylate) and 51 µ2 of methyl methacrylate together with the silane derivative and polymeric dispersant described in Example 5- slurry is heated to 100 ° C for 5 minutes, cooled and then initiated and cast as described in Example 1. The mold is rotated during casting to counteract precipitation. The cast thus obtained has a rough surface due to the presence of the coarse silica particles. The mechanical properties of the product are given in Table II.

39 DK 152215B

Comparative Example I

A ball mill is provided with coarse sand, monomer and other components as described in Example 5? but the mixture is comminuted only for 2 hours instead of for 2b hours. A slurry is obtained which has particles with the following size distribution:

10 micron or less particles $ 98 by number ($ 7 weight)

50 micron or less particles - ($ 29 wt)

100 micron or less particles - ($ 55 wt)

Particles of 250 microns or less - (96 wt $) 10 The surface area of the particles determined by nitrogen adsorption is 0.16 m / g. As the slurry is precipitated too quickly for direct casting, poly (methyl methacrylate) is added and the methyl methacrylate monomers are evaporated to produce a manageable syrup in which the ratio of polymer to monomer is 1: 6.6. The syrupy slurry is then heated to 100 ° C for 5 minutes, cooled, initiated, cast as in Example 1 and cured in a rotary form to counteract precipitation. The finished plate has a rough surface due to the presence of coarse sand particles. The mechanical properties of the product are given in Table II. |

Table II

20 Bending Bending

Particle size module strength- Impact strength (weight $) GN m "^ MN m ~ ei KJ m" ^

Ex. 8 55 $ 10 microns 13.0 120 6.3 100 $ 30 microns 25 Compare- 55 $ 100 microns 10.9 71 3? For 98 $ 250 microns

Compare- 50 $ 200 microns 957 37 2, Rining's ex H 99 $ * + 50 microns

The above compositions illustrate that by using 30 coarse particles, in addition to problems with handling coarse slurries, inferior mechanical properties are obtained in comparison with the properties of products of the invention as exemplified in Example 8.

40 DK 152215B

Examples 12, 13 and 1 * +

The procedure of Example 5 is repeated, except that the concentration of silane derivative is increased to 1.5% by weight based on silica. Before curing, the methyl methacrylate concentration is adjusted such that si = 5 the final concentrations in the cured castings are 50 volume #, 55 volume # and 60 volume # (67 weight #, 72 weight # and 78 weight #, respectively). The mechanical properties of the cured products are given in Table III.

Table III

Taber abrasion; Bending Bending weight removed in 1 g Volume # module strength Impact strength mg / 1000 periods

Example silica GK m "^ MK nr2 KJ m-2 at χοοο g weight 12 50 12 128 6.3 13 56 lf, 8 135 6.1

Ih 60 15.3 150 6.1 13 1 5 S equation for example F 0 3 100 6-8 99

The above results illustrate how the mechanical properties of the cured composite products continue to improve as the particle volume increases. The wear results show a further 7-fold improvement over the base polymer.

Comparative Example J

An attempt to prepare a sample of material according to the method described in Examples 12-1 * + at a 60 # 25 volume fraction of silica using the silane derivative, but omitting the polymeric dispersant results in a cracked cast with errors.

Example 15

Using a similar comminution method as in Example 5, 2726.50 g of coarse β-cristobalite silica sand, average size 200 microns, 903> 85 g of methyl methaerylate (containing 100 parts per million "Topanol" A), 7.8 l of γ-methacryloxypropyltrimethoxysilane are transferred. and 57.989 g of a 98: 2 methyl methacrylate / methacrylic acid copolymer dispersant.

4i DK 152215 B

t ring agent for a 9 liter ball mill with 9.7 g of steatite balls. The mill is rotated for 20 hours at 60 rpm, then 25 g, 32 g of rutile titanium dioxide pigment is added. The mill is rotated for a further b hours, after which the dispersion is separated from the balls. The liquid dispersion contains 77? 8 weight of cristobalite silica and pigment particles. The particle size distribution after comminution is:

10 micron or less particles $ 99 by number ($ 70 wt)

50 micron or less particles - ($ 99 wt)

Particles of 75 microns or less - (100% by weight) 10 To 309 parts of the dispersion are added 1.18 parts of "Perkadox" Yl6 initiator and then evaporated to 9,6 + parts of methyl methacrylate. The dispersion is molded into a stainless steel plate coated with an abrasive and then cured as described in Example 1. A glossy, flawless plate containing 6H volume $ (8l weight $) of silica and rutile particles is obtained. The mechanical properties of the product are: Flexural modulus Ιβ, βΟ GN m-2, flexural strength 139? 7 MN m- ^, impact strength ^, 9 KJ m- ^.

Examples 16-17 In these examples, the dispersion of the inorganic filler in the polymerizable liquid is stabilized by in situ formation of the calcium salt of an acidic copolymer dispersant.

Example 16

A mixture of 1333-5 g of coarse β-cristobalite sand as described in Example 15, 3) 82 g of γ-methacryloxypropyltrimethoxysilane, 120 g of rutile titanium dioxide, 1 g, 15 g of a 25: 1 molar ratio copolymer of methyl methacry = 25 lat and methacrylic acid , 0.36 g (1 molar equivalent of acid contained in copolymer dispersant) calcium oxide, 556.7 g methylmethacry = lat (containing 100 parts per million "Topanol" A) is transferred to a 4.5 liter ball mill together with 5,200 g of steatite beads, and the mill is rotated for 2b hours to produce a dispersion containing 73% by weight of 30 particles with a similar particle size distribution as in Example 5 · The dispersion has a Brookfield viscosity at 2 rpm and 20 ° C of 0.08 Pa.s. A similar dispersion prepared without the calcium oxide has a viscosity of 33 poise at 2 rpm. To 28Ο parts of the first described dispersion are added 2k parts of methyl =

_l I

42 DK 152215 B

methacrylate and 2.0 parts "Perkadox" Yl6 initiator. At this time, the Brookfield viscosity is 0.02 Pa.s. The dispersion is cast and cured as described in Example 1 to produce a glossy sheet containing 50 volumes of silica and rutile and having the following mechanical properties: Bending module 10.55 GN m} bending strength 113 MN m, impact 2 strength 5 KJ m.

Example 17

To 280 parts of the ball-milled dispersion described in Example 15j, 22.32 parts of a * + 5 weight solution of a 90:10 10 weight ratio methyl methacrylate / butyl acrylate copolymer in methyl methacry = lat monomer and an additional 1.78 parts of methyl methacrylate monomer are added. 1.8 parts "Perkadox" Yl6 initiator. At this point, the Brookfield viscosity of the dispersion is 53 poise at 20 rpm and 20 ° C.

The dispersion is cast and cured as described in Example 1 to produce a glossy plate containing 50 volumes of silica and rutile and

ISLAND

with the following mechanical properties: Bending module 10.80 GN m, bending strength -2 MN 112 m, impact strength 5 KJ m.

Example 18 20 The undulating is transferred to a 114 liter ball mill containing 60 volum but $ 9 mm steatite balls:

Coarse cristobalite sand (as described in - Example 15) 2,609 parts

Methyl methacrylate (containing 100 parts 25 per million "Topanol" A) 1.0 + 5 parts 95: 5 weight ratio methyl methacrylate / di = methylaminoethyl methacrylate copolymer MTr 50,000 (GPC) 26.3 parts w γ-methacryloxypropyltrimethoxysilane 7? 1 parts 30 Distilled water 1.5 parts

The volume ratio of the charge to the cavity between the spheres is 1: 1.

43 DK 152215B

The mill rotates at 60 rpm for 6 1/2 hours. A dispersion is obtained in a yield greater than 9 ° with a cristobalite particle size distribution similar to that of Example 5. It contains 70 weight island (50 volume) of finely divided cristobalite and it has a Brookfieldvis 5 quality at 2 rpm at 20 ° C of 5 mPa.s. Evaporation of some of the methyl methacrylate gives a 78 wt fo (55.6 vol.) Dispersion having a viscosity of .04 Pa.s.

To the dispersion with 70 weight dry matter is added as an internal abrasive 0.15 weight island calculated on the dispersion of an alkanolamine neutralized fatty acid phosphate sold under the designation "Zelec" NE (du Pont) and 2 weight island calculated on the methyl methacrylate of "Perkadox" Y16. The dispersion is cast in a glass plate mold and cured as described in Example 1.

A glossy, flawless plate is obtained containing 5 * + volume silica _o and having the following mechanical properties: Bending modulus 12.1 GN m, bending strength 1 ^ -0 MN m ", impact strength 8.0 KJ m".

Example 19

Transferred to a mill 'the following: i

Rough, tunnel-calcined kaolin, average particle dryness 200 microns ("Molochite" 60-80) * 32 ^, 00 g

Methyl methacrylate (100 parts per million "TopanolMA) 113.00 g of γ-methacryloxypropyltrimethoxysilane 0.6 g of 98: 2 copolymer of methyl methacrylate and meth = 25 acrylic acid, M 100,000 (G.P.C.) 9 mrasteatite.

W

spheres 1,050.00 g The mill is rotated for 2k hours at 90 rpm to produce a liquid dispersion containing 76.3 wt. of finely divided calcined kaolin. Finally, the particle size distribution in the dispersion is: 30 Particles of 10 microns or less 99? 5 $ by number (70 weight island)

Particles of 50 microns or less - (93 weight island)

75 micron or less particles - (975 5 weight island)

Particles of 100 microns or less - (100.0 weight island)

44 DK 152215 B

The dispersion is diluted with additional methyl methacrylate, initiated, cast and cured as described in Example 1 to produce a flawless plate containing 50 volumes of inorganic particles with the following mechanical properties: Bending modulus 13.6 GN m, bending strength 130 MN m ~ ^, impact strength 6.6 KJ m "* ^.

* "Molochite" is a registered trademark of English China Clay Limited for a blend of $ 56 mullite and bkfo amorphous silica.

Example 20

Transfer to a 4.5 liter ball mill: 10 Coarse alumina trihydrate (80 $ BS in 300; bound water 3 * + weight $, free water 0 weight $) 1.1 * 52.00 g of γ-methacryloxypropyltrimethoxysilane 3.80 g

Dispersant copolymer as described in Example 19, 16 g 15 Methyl methacrylate (100 parts per million "To = panol" A) 556.8 g 9 mm steatite beads 5,200.00 g

The mill is rotated for 10 hours at 60 rpm. per minute to prepare a finely divided, low viscous dispersion containing 72% by weight of alumi = 20 nitric oxide trihydrate in methyl methacrylate. The dispersion is initiated, cast and cured as described in Example 1 to produce a glossy, flawless plate with the following mechanical properties: Bending module · 13.8 GN

p p m ", bending strength 80.7 MM m ~. The plate does not catch fire when placed in contact with a bunsen burner flame for 1 minute.

Example 21

The procedure of Example 5 is repeated, but the following reactant amounts are transferred to the mill:

Coarse β-cristobalite sand as described in Example 15 2.1 * 78,600 g Rutil titanium dioxide pigment 223,000 g

Methyl methacrylate (100 parts per million "Topanol" A) 1.0 µ * 5,000 g

45 DK 152215 B

γ-methacryloxypropyltrimethoxysilane 7? 1 ° 0 g

Dispersant copolymer as described in Example 19 26,300 g 9 mm steatite spheres 9 * 700,000 g 5 After rotating the mill for 2 h, a dispersion of 73.5 wt. Of cristobalite and rutile in methyl methacrylate having a Brookfield viscosity of 0.35 Pa.s is obtained. 20 ° C and 20 rpm. The particle size distributions of the dispersion are as follows:

Particles of 10 microns or less 99 µl calculated by number (30.0% by weight) 10 Particles of 50 microns or less - (95.5 vsgt ^)

75 micron or less particles - (100.0 wt? 0

After diluting the dispersion with additional monomer to a Brookfield viscosity of 0.04 Pa.s at 20 rpm and 20 ° C and initiating and curing as described in Example 1, a plate containing 50 volumes of cristobalite and rutile is obtained. . The mechanical properties are: -2 -2 Bending module 10.6 GN m ", bending strength 118.9 MN m, impact strength 5.9 KJ m-2.

r

Example 22

The dispersions described in Examples 20 and 21 are mixed in 20 weight ratios of 2: 1, respectively, then initiated and cured as described in Example 1. The cured cast has the following mechanical properties: - 2 - 2 ber: Bending modulus 12, ½ GN m ~, bending strength 102 MN m ~. When one end of a 9.8 cm long x 1.1 cm wide rod of the material is held horizontally in contact with a bunsen burner flame for 1 minute, the material ignites and burns with a small blue flame which extinguishes itself in within a few seconds.

Example 23

To 1,600 parts of the ball-milled dispersion of Example 21 are added * + 3 parts of polyvinyl chloride particles ("Corvic" P65 / 5O), followed by evaporation of ^ 3 parts of methyl methaerylate monorers. The polyvinyl = chloride particles form an organosol dispersion in the methyl methacry = lat monomer. The dispersion is cast and cured as in Example 1 to produce a glossy, flawless plate containing 53.6 volumes ^

46 DK 152215 B

cristobalite and rutile in a matrix of polymethyl methacrylate and polyvinyl chloride. The product has similar mechanical properties and surface appearance as described in Example 21. In a firing test conducted as described in Example 22, a sample burns much slower than the product of Example 21.

Corvic P65 / 5O is a registered trademark of Imperial Chrmical Industries Limited for a spray-dried emulsion polymerized polyvinyl chloride.

Example 2b 10 This example illustrates the effect of crosslinking to accelerate the curing of the liquid material and counteract the boiling of monomer.

To the 321 g of the dispersion of Example 21 are added 2 g, 2 g of methyl meth = aorylate, 6.0 g of ethylene glycol dimethacrylate and 2.36 parts of "Perkadox" Y16.

The dispersion is cast in a preheated flat plate mold in an oven at 80 ° C. After 6 1/2 minutes, a firm, flawless cast is removed from the mold. The temperature inside the mold reaches a maximum of 15 * + ο0. The mechanical properties of the product are as follows: Bending module 13 GN m, bending strength —2—2 strength 128 MN m ”, impact strength b, 3 KJ m".

By repeating the above procedure but omitting the ethylene glycol di methacrylate, the formation of a bubbled and blown cast is achieved.

Example 25 The procedure of Example 2b is repeated with a mold and oven temperature of 90 ° C. After only b minutes, a firm, flawless cast is removed from the mold. The maximum temperature reached is 155 ° C.

Example 26

This example illustrates the "heat lowering" effect of the inorganic particles in preventing monomer boiling during the curing operation.

The dispersion of Example 21 is adjusted by removing such an amount of volume so that the total volume of cristobalite and rutile in matter is measured.

47 DK 152215B

the rial after curing will be $ 60. The dispersion is initiated with 2 $ "Perkadox" Yl6, calculated on the free methyl methacrylate present, and cured at 80 ° C as in Example 2½. After 10 minutes, a firm, molded plate is removed from the mold. In contrast, a plate containing 50 volumes of filler and cured under these conditions is largely filled with failure and blown.

Examples 27-80

These examples illustrate the range of initiators that can be used to cure the liquid materials and that initiator variation 10 has no particular effect on the mechanical properties of the cured products.

Example 2½ is repeated, but the initiators and quantities listed below are used:

Initiator Curing-Bending-Bending- 15 w / w calculated- Temp. time module strength net of monomer ° C min. GN m- ^ MN m d

Ex.27 2 $ BP, 2 $ DMPT 23 ° C 10.6 116

Ex.28 0.5 $ Yl6.0.5 $ ADIB 80 ° C 10 10.16 109

Ex.29 0.5 $ IPP, 0.5 $ DCP 80 ° C 9 10.56 11½

Example 30 0.1 $ IPP, 0.9 $ BP 80 ° C 13 10.9½ H1 BP = benzoyl peroxide DMPT = dimethylparatoluidine

Yl6 = "Percadox" Yl6 = bis- (½-tert-butylcyclohexyl) -per = oxydicarbonate ADIB = 2,2-azo-bis-isobutyronitrile IPP = diisopropylperoxydicarbonate DCP = dichlorobenzoyl peroxide.

Example

This example illustrates the use of a rotational molding method.

To 30Qg of the ball-milled dispersion described in Example 213 is added an additional 11.3g of the dispersant which is

48 DK 152215.B

written in Example 19, 5.5 g of ethylene glycol dimethacrylate, 8.7 g of methyl = methacrylate, 1.6 parts of benzoyl peroxide and 1.6 parts of dimethylparatoluidine. The Brookfield viscosity of the dispersion thus obtained is 4.0 Pa.s at 20 rpm and 20 ° C. The dispersion is placed in a closed 0.57 liter polypropylene cone stub shape (top diameter 12 cm, bottom diameter 11 cm, length 12 cm. The cone tube is rotated about the axis of symmetry at 7.0 rpm and about the end-to-end axis at 16.5 rpm After 30 minutes, a flawless, thin-walled cast is obtained which accurately reproduces the inner contours of the mold.

Example 32

This example illustrates the preparation of a fiber-modified composite material.

The curable material used is the dispersion described in Example 21 with a Brookfield viscosity of 0.04 Pa.s at 20 rpm and 20 ° C, with added initiator and prepared for molding to produce a hardened plate with a 50 volume ^ content of cristo = balit and rutile. This dispersion is pumped at a very low pressure height (less than 69 KPa using a peristaltic pump to the bottom of a vertically placed 4; / 5 mm thick, flat plate containing two 20 layers of cut fiber mats ("Supra" E Mat 1 FPL) and two layers of fiberglass veil were continued until the dispersion flowed out of the top of the mold. The mold was closed by closing the inlet and outlet and the sample was cured in the mold for 2 hours at 50 ° C followed by 2 hours. at 80 ° C.

The finished cured sample was flawless and did not contain entrapped air and contained 56 wt.% Of cristobalite and rutile and 15.6 wt. Of fiberglass wire. The mechanical properties were as follows: Flexural modulus 12.5 GN m-2, flexural strength 95.0 MB m-2, impact strength 27.0 KJ m-2.

"Supra" E Mat is a registered trademark of Fiber Glass Limited 30 for a polymer, latex bonded fiberglass mat with approx. 200 fibers per thread. Each fiber has a diameter of approx. 10 microns.

Comparative Example K

An attempt is made to inject it into Comparative Example I.

49 DK 152215B

written slurry containing particles of over 100 microns in a glass fiber filled form under the conditions described in Example 32. The mold is blocked very quickly and no further slurry can be injected. Another attempt is made by reducing the concentration of silica in the slurry to * + 0 volume ^, but the mold is still blocked.

Example 33 381 g of the dispersion described in Example 2k (50 volume of cristobalite and rutile in the cured product) is initiated with 2.5 g of bone = 10 zoyl peroxide and 2.5 g of dimethylparatoluidine. The dispersion having a Brookfield viscosity of less than 5 poise at 20 rpm and 20 ° C was then placed in a tubular form as described in Example 31? which is lined with one layer of surface veil and one layer of continuous filament fiberglass (FPlAt55 ex. Fiber Glass Limited; each thread contains approx.

1 5 20 micron fibers). The closed mold is rotated at room temperature for 1 hour in the same manner as described in Example 31 *

A fiber-reinforced, thin-walled cast is obtained, which completely soaks the fibers and accurately reproduces the contours of the mold.

EXAMPLE 3 20 A clear, oriented, 8 mm thick, cast polymethyl methacrylate plate ("Perspex'1 ex ICILtd.) Was placed against one side of a 4.5 mm thick hollow plate. Two layers of wire mat as described Example 32 was placed in the mold and the mold parts were then closed in. The dispersion from Example 32 is pumped into the mold in the manner described in this example.

After curing for 10 minutes at room temperature and post-curing at 80 ° C, a high quality 4.5 mm thick casting consisting of a fiberglass reinforced composite material according to the invention is attached to the acrylic sheet. The mechanical properties are as follows:

Acrylic surface Acrylic surface in tension -2 Bending module, GN m "6.5 6.3 -2 Bending strength, MN m 115 109

Impact strength, KJ m- ^ 22.5 21 *

50 DK 152215 B

Example 35

The dispersion of Example 21 is modified by the addition of additional methyl methacrylate to produce a dispersion which, after casting and curing as described in Example 1, yields a 3.3 mm thick sheet containing 30 volumes of cristobalite and rutile. This plate is heated to 180 ° C in an air oven and then fixed over a 10 cm diameter hole and compressed air is applied to one side of the hole and a 9 cm high bubble is blown without breaking the material. The thickness of the top of the bubble is approx. 0.2 mm.

Example 36

A 3.3 mm thick plate is cast from the dispersion described in Example 21 containing 50 volume of cristobalite and rutile. The plate is then heated to 180 ° C and blow molded as described in Example 35. A 6 cm high bladder is formed without breaking the material.

Example 87

An unsaturated polyester resin containing an amount of monocarboxylic acid terminated polymer chains capable of acting as the polymer dispersant and free of dicarboxylic acid terminated chains which may act as flocculants is prepared (using 20 glycol excess) by condensing the following ingredients :

Isophthalic acid 26 parts

Maleic anhydride 32 parts

Propylene glycol k 2 parts, with toluene as a water-containing solvent. Glycol-25 loss is prevented by the use of a short Vigreux column. The reaction is continued until the acid value of the mixture drops to 10 mg KOH / g when 11.5 parts of developed water has been collected. To further reduce the chance of the presence of a dicarboxylic acid terminated chain, 3.8 parts of "Cardura" E * are added and the reaction mixture is maintained at ca. 230 ° C, 30 until the acid value drops to approx. 1.0 mg KOH / g when approx. 1 chain in every 20 is terminated with acid groups. The portion is cooled to below 80 ° C and a vacuum is applied to remove as much toluene as possible and dilute the reaction mixture to ca. $ 70 solids with styrene for up-

51 DK 15 2 215 B

reaching a viscosity in the vicinity of 13 poise, a hydroxyl value of approx. 25 mg KOH / g non-volatile resin and an average polyester molecular weight of approx. 2,000 to 3,000. To this product is then added 0.02 $ "Topanol" 35 * + calculated on solid resin.

A 50 volume $ silica dispersion in a polyester resin with 50 $ non-volatiles in styrene is prepared by transferring the following to a kneading mixer and mixing for 2 hours:

Finely divided silica ("Minusil" 30 ***) 312 parts 68% by weight solution of polyester in the styrene prepared as described above 89.3 parts

Styrene 33? 9 parts γ-methacryloxypropyltrimethoxysilane 2.98 parts 1 $ solution of hydroquinone in styrene 1.0 parts

A low viscous, deflocculated dispersion containing 71 wt. $ 15 silica is available, which self-emits air and is self-leveling. The dispersion is initiated with 1.5 $ benzoyl peroxide based on the resin and styrene present. After casting in a glass plate mold and curing at 80 ° C for 1 hour, a high quality plate is obtained. Viscosities and mechanical properties are given in Table IV.

20 * "Cardura" E is a registered trademark of Shell International for a glycidyl ester of a branched C ^-C- saturated fatty acid with a typical epoxide value of 2 * + 5.

"Topanol" 35 * + is a registered trademark of Imperial Chemical Industries Limited for 2,6-di-tert-butyl-1 + -methoxyphenol.

25 "Minusil" 30 is a registered trademark of Pennsylvania Glass

Sand Company Limited for dry milled air-classified oc-quartz silica with the following particle size distribution:

Particles of 10 microns or less $ 99j8 calculated on number ($ 52 wt) 30 Particles of 50 microns or less ($ 86 wt)

100 micron or less particles ($ 100 wt)

Example 38 The following ingredients are transferred to a kneading mixer and mixed for 2 hours:

52 DK 152215B

"Minusil" 30 * 312 parts

Solution of polyester in styrene (as described in Example 37) 50 parts

Styrene 65 parts 5 γ-methacryloxypropyltrimethoxysilane 2.98 parts 1 fo hydroquinone solution in styrene 1.0 parts

A very low viscous, deflocculated dispersion containing 72% by weight of silica is formed upon curing as described in Example 37j and a high quality casting is obtained. Viscosities and mechanical properties are given in Table IV.

&

See the explanation in Example 37 ·

Example 89

The procedure of Example 38 is repeated, but the silane derivative is omitted. A very low viscosity dispersion and a high quality cast are formed. Viscosities and mechanical properties are shown in Table IV.

Comparative Examples L and M

The procedures of Examples 37 and 38, respectively, are repeated using an isophthalic acid-based polyester of similar composition, but with an acid value of 25 mg KOH / g (non-volatile). This relatively high acid value of poly = 20 esters, which is typical of commercially available polyesters, shows that it contains a substantial amount of short dicarboxylic acid terminated chains which act as flocculants rather than dispersants. In each case, a dispersion containing 50 volumes of silica ("Minusil" 30) is prepared. The relatively higher viscosities of the obtained dispersions as shown in Table IV clearly show that the dispersions are flocculated.

Comparative Examples N-Q

These examples illustrate the compositions described in Examples 37-39 and Comparative Example M when the silica filler 30 is omitted. The curing conditions used are those described in Example 37. Viscosity data and other results are shown in Table IV.

53 DK 152215B

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54 DK 152215 B

From the results in Table IV, it is clear that the low acid value polyester with low probability of containing difunctional acid forms gives rise to much lower viscosity dispersions than the high acid polyester. Upon curing, the liquid gives 5 materials according to Examples 37? 38 and 39 composite materials which are stronger than the polymer matrix. This effect is most noticeable with polyester material with 30 $ non-volatile material, for the non-filler 30 $ NV polyester hardener not even for a homogeneous solid.

Example kO

This example and Examples 1 to 2 illustrate the use of a polymer matrix derived from methyl methacrylate and the bis (methacrylic acid) adduct of an epoxy resin.

1.6 ^ + 0 parts of a finely divided β-erystobalite silica having a surface area of o 15 3 m / g and a particle size distribution as follows:

5 micron or less particles - (* + 0 wt $)

Particles of 10 microns or less 99? 9 $ by number (81% by weight) Particles of 50 microns or less - (100% by weight) are dispersed in a mixture of 120 parts of methyl methacrylate and U-80 parts of 20 for a $ 50 solution in methyl methacrylate of a bis (methacrylic acid) adduct of the epoxy resin known as "Epikote" 100 µ (registered trademark), which is a condensation product of epichlorohydrin and diphenylol propane having a molecular weight of approx. 1800, in the presence of cow portions of a solution of a dispersant as described below. The dispersion is carried out using a laboratory high-speed Torrance Cavitation Disperser, adding the silica little by little while stirring the monomer / adduct mixture, and finally using 1000 rpm for 30 minutes to complete the operation. . A liquid dispersion is obtained, the viscosity of which is measured by a Brookfield viscometer, multispeed model RVF (Brookfield Engineering Laboratories Inc., Massechusetts, U.S.A.). In a portion of the dispersion, 2% by weight "Perkadox" Yl6 initiator is dissolved based on the monomer / adduct content, the material is degassed under reduced pressure and then molded at 50 ° C for 2 hours and then at 80 ° C for 2 hours to form a -35 those of composite material containing 5 * + volume $ silica. Physical and

55 DK 152215 B

mechanical data for this example are given in Table Y. In this and the following examples, viscosities are expressed in poise at 20 ° C. Where in the case of shear-thickening or shear-thinning compositions two viscosity values (a) and (b) are indicated, they are marked with 5 (a) at 2 rpm using the Brookfield spindle size and those with (b) is measured at 20 rpm again using the indicated spindle size. Where, in the case of essentially Newtonian materials, only one viscosity value is given, this is measured at 2 rpm.

The bis (methacrylic acid) adduct of the epoxy resin used in the above process is prepared by heating the following ingredients at reflux at 135-100 for 1 1/2 hours: "Epikote" 100> + 720 parts 15 Butyl acetate 500 parts

Hydroquinone 0.1 part

Dimethylaminoethanol 2 parts

Methacrylic acid 70 parts In this way, 90 $ of the 20 epoxide resins present in the epoxy resin are converted to ester groups by the methacrylic acid as shown by acid value measurements. The solvent is removed under reduced pressure at 70 ° C and the residue dissolved in methyl methacrylate to prepare a $ 50 solution.

The dispersant solution used in the above procedure is prepared as follows. The above-described preparation of the epoxy resin adduct is followed, but the methacrylic acid amount is reduced to 50 parts. To the product, 33 parts of p-nitrobenzoic acid and 1 part of dimethylaminoethanolo are added without removing the solvent. The mixture is heated to reflux for 135-100 ° C for 2 1/2 hours, then the solvent is removed at 70 ° C under vacuum. The resulting dispersant is dissolved in methyl methacrylate to prepare a 50 µl solution.

Comparative Example E

The procedure of Example is repeated, but dispersant solvent

56 DK 152215 B

the omission. Viscosity measurements on the dispersion obtained show that it exerts a significant shear thickness. These data and properties of the cured composite are given in Table V.

Example * + 1 The procedure of Example ^ 0 is repeated, but immediately before the final step of dispersing silica at 1000 rpm for 30 minutes, γ-methacryloxypropyltrimethoxysilane and water are incorporated in quantities of k parts and 1 part to 2.2 ^ 0 parts respectively. of the silica / monomer / adduct mixture. The physical and mechanical properties measured are listed in Table V.

^ The compound

Viscosity of the properties of materials flowing- Bending- Bending- Stroke-

Material material_ module strength strength

Ex. No. type (a) * (b) * GR m "^ MN m" 2 KJ No. 2 "0 Presence- 129 129 12.0 88.5 * +, 0 the dispersant

Compare- No dispersion- 100 M + 0 13) 7 109 5, * +

nings.eks. mashing agent R

i + l Dispersant 22 89 12.5 130.7 6.6 agent and interface binding agent * (a) measured with Brookfield spindle # 2.

(b) measured with Brookfield spindle # 5 or # 6.

The results set forth in Table V show the marked improvement in the flowability of the curable material resulting from the use of the polymeric dispersant, and also the further improvement of flowability obtained by incorporating an interface binder during the dispersion of the filler.

Example b2

The procedure of Example kO is repeated but as starting materials used.

57 DK 152215B

1.6H0 parts of finely divided silica, 120 parts of methyl methacrylate, 310 parts of the 50% solution of the epoxy resin adduct, 170 parts of a dispersant solution as described below and 1 part of water are used.

The dispersion obtained has viscosities of (a) 6.6 Pa. s (spindle no.

5 3) and (b) 37.8 Pa..s (spindle # 6). The cured composite material containing 5 µm volume of silica has a flexural modulus of 15.1 GN m ", flexural strength of 15 * + MN m" and a impact strength of 759 KJ m.

The dispersant solution used in this process is obtained as follows. The procedure described in Example * + 0 in connection with the preparation of the epoxy resin adduct used therein is followed except that the amount of methacrylic acid is reduced to 50 parts.

To the $ 50 solution of the adduct, 35 parts of Y-aminopropyltri = methoxysilane are added and the mixture is allowed to stand overnight to complete the reaction of the residual epoxide groups of the adduct with the amino groups of the silane derivative.

Examples of-3

This example illustrates the use of a polymerizable system based on styrene and chlorophenylmaleimide.

312 parts of chlorophenylmaleimide dissolve in 208 parts of styrene under low heating to give a 1: 3 molar comonomer mixture. To this are added 26 parts of a 50 $ solution of a dispersant as described below, followed by 11/10 parts of the finely divided silica described in Example MD. The silica is dispersed in the manner described in Example * + 0, adding immediately before the final step of the dispersion at 1000 rpm, 3.5 parts of γ-methacryloxypropyltrimethoxy® silane and 0.7 parts of water. A liquid dispersion (viscosity Q; 9 Pa.s) is obtained which can be cured as described in Example * + 0 to prepare a composite material plate containing 53.7 volume of silica.

The dispersant solution used in this example is obtained as follows. To a mixture of 0.85 parts of butanol, 2.0 parts of glycidyl = methacrylate and 17.8 parts of hydroxyisopropyl methacrylate heated to 30 ° C, 2.55 parts of methacrylamide are added together with a small amount of water to promote the solution. 13.2 parts of styrene, 20.1 parts of 2-ethylhexyl acrylate and 0.5 parts of tertiary-butyl perbenzoate are then added. k2.2 parts of xylene 35 is heated to reflux temperature (1 + 0 ° C) and the previous mo =

58 DK 152215B

number mixture is added over a period of 3 hours with the addition of an additional 0.1 part of tertiary-butyl perbenzoate after 1 hour. Heating at the reflux temperature is continued until the mixture has a solids content of 5 + 9-51 $. The mixture is then cooled to 5 to 110 ° C and 0.6 parts of p-aminobenzoic acid and 0.1 parts of "Armeen" DMCD (registered trademark for dimethyl cocosamine) are added. Reflux heating is repeated again and continued until the mixture has an acid value below 0.5 mg KOH / g. The xylene is then removed by vacuum distillation and the remainder of the solid polymer is dissolved in styrene to prepare a 50 $ solid solution.

Comparative Example S

The procedure described in Example 5 + 3 is repeated, but the dispersant solution is omitted. When only 32 volumes of silica has been added, the dispersion has already become strongly thixotropic and 15 cannot be cast.

Example 5 + 5 +

This Example and Example * + 5 illustrate the use of a polymerizable system based on methyl methacrylate copolymerized with a reaction product of hydroxyethyl methacrylate and a melamine-formaldehyde resin.

A mixture of 180 parts of paraformaldehyde, 126 parts of melamine, 185 parts of n-butanol and 200 parts of water is adjusted to pH 9.0 using 0.5N sodium hydroxide solution and then refluxed for 30 minutes. To this mixture are added 780 parts hydroxy = 25 ethyl methacrylate (this contains sufficient free methacrylic acid to lower the pH of the mixture to 5 +, 5), 0.5 parts hydroquinone and 200 parts toluene. The mixture is heated and water is removed by distillation using a Dean and Stark separator. When distilled for 3 hours, the temperature of the mixture is raised from 88 ° G to 120 ° C and 315+ cm ^ 30 aqueous distillate is removed. The product is filtered to give a low viscous syrup. Then, by the method described in Example 5 + 0, a dispersion is prepared from 1,210 parts of the finely divided silica described in Example 5 + 0, 125 parts of the syrup described above, 375 parts of methyl methacrylate and 20 parts of the example described in Example 18 me = 35 methyl methacrylate dimethylaminoethyl methacrylate copolymer dispersant

59 DK 152215B

medium «A very liquid dispersion is obtained. The properties of the dispersion and the properties of a composite material containing * + 8.0 volume of silica made therefrom by curing are given in Table VI.

Example 1 + 5 The procedure of Example kb is repeated, but immediately before the final stage of dispersion at 1000 rpm for 30 minutes, 5 parts of γ-methacryloxypropyltrimethoxysilane and 1.25 parts of water are added. The properties of the dispersion obtained and the composite material obtained are listed in Table VI.

Comparative Example T

The procedure of Example kk is repeated, but the copolymer dispersant is omitted. The dispersion quickly becomes thixotropic during the addition of silica and only * + 6.6 volume ^ silica can be introduced. The properties of the dispersion and the derived composite are listed in Table VI.

Table VI

The compound

Viscosity of material properties of flow - Bending - Bending - Stroke - Material - material module strength strength

Ex. No. type of all Pa.s GN m „^ MN m„ ^ KJ m- 1 + 1 + Presence- Q, 085 12.23 81) 9 3) 21 the dispersant 1 + 5 Dispersion 0.074 11.81 119 5.55 Agent + Interface Charge Binder

Comparison - Neither Dispersion, 65 11.1 + 8 66.9 3.13 Ex. tester or binding agent

Here again, the results show the marked improvement of the flowability of the curable material and of the properties of the derived composite material obtained by the incorporation of the polymeric dispersant and further of the interface bonding agent.

Example 6

60 DK 152215B

This example illustrates the use of a copolymer of methyl methacrylate and a vinyl-identified urethane prepolymer as the basis for the polymer base material.

A prepolymer is prepared by dissolving ^ + 00 parts of "Desmodur" N

(registered trademark of a trifunctional isocyanate) in 686 vol. mendele methyl methacrylate together with 0.1 part hydroquinone and 1.0 part dibutyltin dilaurate. 286 parts of hydroxyethyl methacrylate is slowly added over 5 minutes and the mixture is allowed to stand for another 10 minutes (during this time the temperature rises to about 50 ° C).

Then a dispersion is prepared by the method described in Example 100 from 1.3% of the finely divided silica described in Example 100, 220 parts of the above-described prepolymer, 220 parts of methyl = 15 methacrylate, 60 parts of a dispersant solution. as described below and 1.2 parts of water. The dispersion is very liquid with a viscosity of only 2.0 poise and is readily fabricated into a composite material containing 53? 3 volume of silica and having the following excellent mechanical properties: Flexural modulus 12.0½ GN m ", flexural strength 129.6 20 MN m "^, impact strength 6.75 KJ m ~ ^.

The solution of the dispersant used in this process is obtained by dissolving U80 parts of "Desmodur" N in 806 parts of methyl methacrylate together with 0.1 part of hydroquinone and 1.0 part of dibutyltin dilaurate, after which 260 parts of hydroxyethyl methacrylate are added over * + 5 mi-25 nuts, and the mixture is allowed to stand for an additional 1 1/2 hours.

Finally, 72 parts of γ-aminopropyltrimethoxysilane are added and the mixture is allowed to stand overnight.

Comparative Example U

The procedure described in the example is repeated, but the solution of the dispersant is omitted and the amounts of the prepolymer and the methyl methacrylate are increased to 250 parts each. The resulting dispersion is very viscous and cannot be molded.

Example * + 7

6i DK 152 215 B

This example illustrates the use of polymer matrix based on polystyrene with the filler made by comminution in the presence of a dispersant and an interface binder.

5. 1.26 * + parts of coarse β-crystobalite silica, * + 97 parts of styrene, 3.5 parts of γ-meth = acryloxypropyltrimethoxysilane, 1.0 part of water and 50 parts of a 25 $ solution in the styrene of a dispersant copolymer as described below are milled in a ball mill according to the method described in Example 5. A dispersion is obtained which contains 50.0 vol. 10 of silica and has a viscosity of only 0.06 Pa.

The dispersant is used in a 1: 1 by weight based copolymer of cis-1, + + polyisoprene and poly (dimethylaminoethyl methacrylate), in which both polymer blocks have a molecular weight of 10,000.

Comparative Example V

The procedure of Example * + 7 is repeated, but the dispersant solution and the silane derivative are omitted and the styrene amount is increased to 5 * + 0 parts. The dispersion obtained again contains 50.0 volume of silica, but is viscous and pronounced thixotropic.

Example * + 8 This example and Examples * + 9 and 50 illustrate the use of barium sulfate as the inorganic filler in a methyl methacrylate based system.

I.700 parts Blanc Fixe (a precipitated barium sulfate having a surface area of 3.3 m / g and an average particle size of 0.5-0.6 microns) is dispersed in 500 parts of methyl methacrylate and 20 parts of the copolymer dispersant described in Example 5 using the procedure described in Example * + 0. A very liquid dispersion (viscosity 0.25 Pa.s) is obtained containing * + 3.6 volume $ Blanc Fixe.

Example * + 9 The procedure of Example * + 8 is repeated, but the copo = described therein

62 DK 152215 B

polymer dispersant is replaced by 18 parts of the copolymer dispersant described in Example 18 and the amount of Blanc Fixe is increased to 2.33Ο parts. The dispersion obtained contains 50 volumes of the filler and has viscosities of (a) 33 poise (spindle # 1 +) and (b) 5 14.0 Pa. s (spindle # 7) · A composite material obtained by curing the dispersion has bending modulus 12.0 * + GN m ", bending strength M +, 1 MN m" 2, and impact strength 1.68 KJ m "^.

Example 50

The procedure of Example 1 + 9 is repeated, but 5 parts of meth = 10 acrylic acid are added after complete incorporation of Blanc Fixe. Following this addition, an immediate and substantial increase in the flow rate of the dispersion is seen. The dispersion has a viscosity of only 0.10 Pa.s, and a composite material obtained therefrom by curing has a bending modulus of 8.98 GN m ", bending strength 1 + 8.9 MN m" and impact strength of 1.93 KJ m ". The improved flow rate of the dispersion can be attributed to the conversion of the tertiary amine anchor groups in the dispersant copolymer to the corresponding methacrylic acid salt groups.

Comparative example ¥

The procedure of Example 1 + 8 is repeated, but the copolymer dispersant is omitted. After the addition to the methyl methacrylate of only 15 volumes of Blanc Fixe, the dispersion becomes so sluggish that further addition of filler is impossible.

Example 51 In this example and Example 52, the polymer matrix is derived from a styrene-divinylbenzene-butyl hydrogen maleate copolymer.

I.300 parts of the finely divided silica described in Examples 1 + 0 are dispersed using the method described in this example in 180 parts styrene, 20 parts divinylbenzene (as a 5kg solution in ethyl = vinylbenzene), 3 0 parts of butyl hydrogen maleate and 9 parts of the copolymer dispersant of Example 18. The properties of the dispersion thus obtained containing 50 volumes of silica and of a flawless cast plate obtained by degassing and curing the dispersion are shown in Table VII.

Example 52

63 DK 152 215 B

The procedure of Example 51 is repeated with the addition of 5 parts of γ-methacryloxypropyltrimethoxysilane and 1 part of water to the mixture immediately before the final step of the dispersion at 1000 rpm. The properties of the dispersion thus obtained, again containing 50 volumes of silica, and of the derived cured composite material are shown in Table VII.

Comparative Example X

The procedure of Example 51 is repeated, but the copolymer dispersant is omitted. When only approx. b2 volume ^ silica, it turns out that the dispersion is extremely viscous and cannot be molded.

Table VII

The compound

Viscosity of material properties of flow - Bending - Bending - Stroke - Material - material module strength strength Ex. No. type of ale Pa.s GN m „^ MN m- ^ KJ m- ^ 51 Presence- 1.0 l +, 0 16.8 1.7 the dispersant 52 Dispersion 1.0 2.0 13.5 2.8 Agent + Interface Charge Binder

Example 53,970 parts of calcium carbonate white # 16 having the following particle size distribution:

Particles over 20 microns 17 wt $

Particles over 10 microns 30 wt $

Particles over 5 microns 53 wt $

Particles greater than 2 microns by weight are dispersed in 300 parts of methyl methacrylate containing 17 parts of

64 DK 152215 B

Example 18 copolymer dispersant using the procedure described in Example * + 0. The resulting dispersion is liquid, has viscosities of (a) 12.4 Pa.s (spindle # 3) and (b) 3.15 Pa.s (spindle # 3). It can be degassed and molded to a 5 composite plate without difficulty. The filler content is 555 * + volu- men $.

Example

The procedure of Example 53 is repeated with the addition of 5 parts of methacrylic acid after complete incorporation of the calcium carbonate.

This results in an increase in the flow rate of the dispersion, the viscosities being (a) 6.9 Pa.s (spindle # 3) and (b) l »3 Pa-S (spindle # 3) and in easier degassing. and casting.

Comparative Example Y

The procedure of Example 53 is repeated, but the copolymer dispersant is omitted. It seems possible to incorporate only approx. * + 0 volu- men $ calcium carbonate, which is due to the high viscosity assumed by the dispersion.

Example 55 1,600 parts of the finely divided silica described in Example Ho are dispersed by the method described in this example in 500 parts of butyl = acrylate, 0.5 parts of polypropylene glycol dimethacrylate, 3.5 parts of γ-meth = acryloxypropyltrimethoxysilane, 0 , 7 parts water and 13 parts 90:10 copolymers of butyl carylate and dimethylaminoethyl methacrylate as dispersant. A dispersion of viscosity 0.7 poise is obtained containing 25 57? 7 volume of silica which is easily degassed and molded to a plate of composite material.

Example 56

This example illustrates the preparation according to the invention of a composite material in which the polymer matrix is formed by ring opening addition polymerization of epoxide group-containing prepolymers.

* + 0 parts "Epikote" 828 (registered trademark, a deep oxide formed

Claims (8)

65 DK 152215B in the reaction of diphenylolpropane with epichlorohydrin and marketed by Shell Chemical Co.) is mixed with 60 parts of epoxide # 8 (a mixture of glycidyl ethers and C 1-4 monovalent alcohols marketed by Proctor and Gamble) and 5 parts of a dispersant as described below. 2k5 parts of β-crystobalite sand is dispersed in this mixture using a Torrance Cavitation Disperser apparatus. The product is a liquid dispersion (viscosity 2.4 Pa.s) containing 50 volumes of silica. 100 parts of the dispersion is polymerized with the addition of 3 parts of ethylene tetramine to give a rigid, tough, composite material. The dispersant used in this example is prepared by reacting 100 parts of "Epikote" 828 with 10 parts of p-nitrobenzoic acid in the presence of 1 part of dimethylaminoethanol at 1MD-150 ° C for 30 minutes. A similar dispersion prepared by the above method, but omitting the dispersant is much more viscous and consequently much more difficult to use to prepare a satisfactorily composite material. Claims. 1. Stable, liquid, moldable and curable material of a polymerizable organic liquid and particulate inorganic fillers obtained by dispersing a filler (B) in a component (A) in the presence of dispersant (C) and optionally a binder (D), wherein (A), (B), (C) and (D) have the following meanings (A), an organic polymerizable liquid having a viscosity at the forming temperature of the curable mass of a maximum of 5.0 Pa.s, consisting of (Al) a liquid monomer or monomer mixture which, during polymerization or polyadition, can form a solid polymer in which the repeating units of the polymeric chain are joined by CC bonds or with CC bonds which are interrupted by the heteroatoms 0, N or Si, or (A2) a mixture of one or more preformed polymers with one or more monomers, the monomer component of which is under polymerization DK 152215B (A3) a partially polymerized material or a prepolymer which, during polymerization or polyamide, ddition is capable of forming a solid polymer, (B) 20-90 by volume of at least one finely divided inorganic filler having -2, an elastic shear elasticity coefficient of at least 5 GN.m and a maximum particle size of 100 µm, of which at least 95% of the particles have a particle size of not more than 10 µm and a maximum of 10% of the particles have a particle size of not more than 0.1 µm, (C) at least 0.01 µm, calculated on the total surface area 10 of the particulate particles (B), polymeric dispersant having at least one polymeric chain having a molecular weight of at least 500 containing one or more anchorage groups suitable for association with the filler (B), provided that (a) the polymeric chain is selected such that the liquid polymerizable component is selected (A) is solvable to the extent that, as an independent molecule, it exhibits a significantly better solubility in component (A) than in a theta solvent, (b) the polymeric dispersant can be reconciled with the product of the polymerization of components (A) and (c), where appropriate, contains functional groups suitable for grafting or copolymerization with the monomers present in component (A) during the curing operation, (D) low molecular weight binder with one or more to interact with the groups present in component (B) suitable groups as well as one or more groups capable of copolymerizing or graft polymerizing with the polymer formed by the polymerization of the liquid component (A). Material according to claim 1, characterized in that the component (A) consists of an acrylic or methacrylic acid ester. Material according to claim 1 or 2, characterized in that the component (B) is silica or an alumina. Material according to claims 1-3, characterized in that its filler concentration is 35-85% by volume. DK 152215 B Material according to claims 1-4, characterized in that the component (C) is a polymer of the same kind as the polymer obtained by polymerization of the component (A) with a molecular weight in the range of 20,000 to 200,000, which along the polymeric chain 5 have groups which are suitable for association with the particles of the inorganic filler (B). Process for producing a stable, liquid, moldable and curable material according to claim 1, characterized in that the finely divided filler (B) is dispersed in the component (A) in the presence of the dispersant (C) and optionally the binder (D). , so that the filler (B) represents at least 20 volume / µ of the total material. 15 Process according to claim 5, characterized in that the fine particles (B) of fine fill are obtained in situ by comminuting or grinding coarse non-colloidal particles. 2Q Use of the material according to any one of claims 1-5 in multicomponent materials. 25 30 35