THERMAL INSULATING MATERIAL

Abstract: A thermal insulating material comprises a shaped or moulded foamed or expanded solid composite comprising a coal ash and a petroleum resin and/or synthetic thermoplastic resin. Such a material is produced by intimately mixing to­ gether a coal ash such as fly ash and a petroleum resin and/­ or a synthetic thermoplastic polymer in particulate form, in­ corporating a dilute solution of hydrogen peroxide in a quan­ tity sufficient to form a mass having a paste-like mouldable consistency, shaping or moulding the mass to the required shape or shapes and heating for at least 1 hour at a tem­ perature of at least 150°C.

Description: THERMAL INSULATING MAThR1AL The present invention relates to a thermal insulating material and to a process for the production thereof. It is an object of the invention to provide a relatively low cost foaned or expanded thermal insulating material. Insulation materials of thermoplastics such as polyethylene and coal ash are known from Japanese Patent Application 81,131,887 and according to German Patent Application 30 19 215 these may be made from polypropylene and foamed with azo producing blowing agents. We have now found an attractive process for the manufacture of similar materials especially from petroleum resins. According to one aspect of the invention, a process for preparing a foamed or expanded thermal insulating material comprises the steps of intimately mixing together a coal ash and a petroleum resin and/or a synthetic thermoplastic polymer in particulate form, incorporating a dilute solution of hydrogen peroxide in a quantity sufficient to form a mass having a paste-like mouldable consistency, shaping or moulding the mass to the required shape or shapes and heating for at least 1 hour at a temperature of at least 1500C. According to another aspect, the invention provides a thermal insulating material comprising a shaped or moulded foamed or expanded solid composite comprising a coal ash and a petroleum resin and, optionally, a synthetic thermoplastic resin. The coal ash is preferably fly ash which is a product of the combustion of powdered coal, normally using a forced draft. Among the petroleum resins which may be employed are those obtained from the polymerisation of steam-cracked or thermallycracked naphthas. The resins may be aliphatic or aromatic or aliphatic/aromatic am may be the partially or substantially fully hydrogenated oounterpatts thereof. Typical resins may be prepared by the thermal or catalytic, generally Friedel-Crafts, polymerisation of unsaturated feeds, obtained from petroleum cracking such as Cs/C6 olefine diolefine containing aliphatic feeds or the CEJC9 unsaturated aromatic feeds or mixtures thereof. A range of products is comnercially available. The petroleum resin is mixed into the coal fly ash in particulate form, normally of average size not exceeding 5 mm, preferably up to 1 rtia. In addition to, or in substitution for a part or the whole of, the petroleum resin, it is possible to employ a thermoplastic synthetic polymer, for example, an ethylene/vinyl acetate type. Again, the synthetic polymer is employed in particulate form, preferably of average size not exceeding 5 mm. Ihe foaming or expansion agent employed is a dilute solution of hydrogen peroxide. By "dilute solution" is meant not greater than 6 wt > and very preferably not greater than 3 wt . A 3 wt solution of hydrogen peroxide corresponds to 10 volume strength (1 ml of the 3 wt g H202 will liberate 10 ml of oxygen gas on full decomposition and is known as 10 volume H202). in the practice of this invention it is especially preferred to employ 1 to 5 volume hydrogen peroxide. These low volume strengths give rise to a product of slightly higher density and higher compression resistance than higher volume hydrogen peroxides. It has been unexpectedly found that other inorganic foaming agents, for example, ammonium nitrate and sodium tetraborate, do not give rise to utilisable products. The following is a preferred range of relative amounts of components that can be employed: Coal fly ash : 40 to 60 by weight ) Petroleum resin ) ) Total 70 wt > or ) : 30 to 10 by weight ) resin plus ) synthetic polymer ) Hydrogen peroxide : 30 by weight (1 to 5 volume strength) The mixing of the coal ash, petroleum resin and/or synthetic thermoplastic polymer, is normally conducted at room temperature. The hydrogen peroxide solution is then added, forming a paste-like mouldable mass. The thus obtained paste is then placed in a mould and heated. The heating is normally conducted in the range 150 to 2500C; preferably 150 to 200 OC when petroleum resin is employed. When a thermoplastic polymer is used the temperature required may be higher to obtain a substantially homogeneous product. Usually heating is continued for at least 1 hour, and suitably for from 1 to 3 hoards. The formed, shaped product can have a thermal conductivity coefficient of aFproxmmately 0.1 W/m. C. This is only from two to three times higher than that of foamed or expanded polystyrene, and some twenty to thirty times less than that of cellular concrete. Samples of materials made by the process of the invention had good water resistance. There was no increase in weight even after several weeks Bnmersion in water. The fire resistance of samples tested was good, even after heating at 1300 to 1500"C the samples remained essentially in their original shape and did not drop to powder. When in contact with a naked flame no flame propagation occurred on or below the surface. mechanical ocirpression resistance of materials made by the invention is rrrrmally in the range 90 to 110 kPa. The following Examples are given by way of non-limitative illustration of the invention: Example This Example illustrates the effect on relative density (apparent density) of the concentration of the hydrogen peroxide employed, other components being constant. Three different shapes of product were moulded, viz. a cone, a parallelipiped and a cylinder. The test products were moulded from 75 parts by weight of fly ash and 25 parts by weight of a finely ground (1 mn) polyaromatic petroleum resin sold under the Trade Name Escorez 3102 (Ring and Ball softening point 100 C and molecular weight approximately 600). 40 parts by weight of hydrogen peroxide (oxygenated water) of different concentrations were employed. The test. products were heated for 2 hours at approximately 180 C. The results for each moulded shape are shown in graphic form in Fig. 1. The ordinate represents apparent (relative) density and the abscissa the concentration of the hydrogen peroxide solution (oxygenated water) employed in terms of volune strength. In each case increase in hydrogen peroxide concentration was acconpanied by decrease in apparent density up to 5 volume H2. Example 2 A product was obtained from: 75 parts by weight of coal fly ash 25 parts by weight of EVA copolymer 25 parts by weight of 2.5 vol HzO2. The ethylene/vinyl acetate copolymer was one having (i) from 12 to 16 wt % of vinyl acetate and (ii) a melt index of from 2000 to 5000; and was in finely ground (approx 1 mm) form. The pasty mouldable mass obtained was moulded into the shape of a cone and then heated at 2200C for 2 hours. The product had an apparent density of 0.48.

Claims: CLAIMS: 1. A process for preparing a foamed or expanded thermal insulating material, comprising the steps of intimately mixing together a coal ash and a petroleum resin and/or synthetic thermoplastic polymer in particulate form, inoorporating a dilute solution of hydrogen peroxide in a quantity sufficient to form a mass having a paste-like mouldable consistency, shaping or moulding the mass to the required shape or shapes and heating for at least 1 hour at a temperature of at least 150 0C. 2. A process as claimed in claim 1, wherein the coal ash is a fly ash. 3. A process as claimed in claim 1 or claim 2, wherein the petroleun resin particulate size is not more than 1 mn. 4. A process as claimed in any preceding claim, wherein the petroleum resin is a polyaromatic resin. 5. A process as claimed in any preceding claim, wherein the synthetic thermoplastic polymer, widen employed, is in particulate form, preferably of average size not more than 5 mm. 6. A process as claimed in any preceding claim, wherein the hydrogen peroxide solution is less than 10 volume centration, preferably up to 5 volume concentration. 7. A process as claimed in any preceding claim, wherein the heating is conducted at a temperature in the range 100 0C to 250 C. 8. A thermal insulating material comprising a shaped or moulded farmed or expended solid oomposite comprising a coal ash and a petroleum resin. 9. A thermal insulating material according to claim 8 in which the coal ash is a fly ash. 10. A thermal insulating material according to claim 8 or claim 9 which also contains a synthetic thermoplastic polymer.

Inventors: LECORBEILLER, GILBERT MARIE, PARROT, PIERRE ROGER
Applicants: EXXON RESEARCH AND ENGINEERING COMPANY
Application year: 1985
Main classification: C04B26
IPC codes: C04B26