DE2833142A1 - COMPOSITION AND METHOD OF MANUFACTURING FOAMS FROM SOLID, LIQUID MATERIALS USING SELECTED, SOLID, PARTICULAR SUBSTANCES - Google Patents

Description

Sponsorship request

ng. Heknut Gortz \

Frankfcrf am Main 70 'i "

July 27, 1978

5Gzm / Ro 1

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INTERNATIONAL CONSTRUCTION PRODUCTS RESEARCH INC., West End Avenue, Old Greenwich, Ct. 06870, USA

Composition and method of making foams from solid liquefying materials using selected, solid, particulate substances

The present invention relates to foams of solid liquefying materials; the invention particularly relates to a composition and a method for producing such foams using a solid, particulate substance, which can produce a foaming effect if it is added to the liquid earthed material.

Solid, liquefying materials, ie materials that are normally solid but that can be liquefied, can change their physical properties when they change from solid to liquid and back to solid. For example, the density, structural strength and insulating properties of a solid material can be changed by expanding the material with a gas when it is in the liquid state to produce a foam or a cellular solid material as it cures. For example, a method of foaming sulfur was developed by the Southwest Research Institute to produce foamed sulfur for various uses where an economically acceptable, tough, rigid foam is desired. Of the-

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sulfur-like barns have densities in the range of seven PfLind per cubic foot to thirty pounds per cubic foot and higher; in certain applications they can compete with plastic foams and they should because of their higher compressive strengths find additional important application possibilities with similar thermal conductivity values.

To the possible uses, which for sulfur barns Structural elements should be considered where good thermal insulation properties are desirable and, as a consequence of the high electrical resistance and the good dielectric properties is also a use possible as electrical insulating material. In a commercial application of the foam sulfur supplied by the Southwest Research Institute, Chevron Chemicals, Inc. developed "Furcoat", a modified sulfur foam, in the Arctic tested as a pipeline insulation to protect against permafrost; "Furcoat" is also called road bed insulation tested using a foam 2.5 cm thick replacing 30 cm of gravel. The material is said to be on site with a propellant foamed, e.g. carbon dioxide mixed with the modified, molten sulfur that causes the gas to solidify occluded.

Chemical or physical foaming agents, also known as blowing agents, have long been used to make plastic foams to manufacture. These solid, liquid or gaseous substances create a cellular structure, by gas formation in the material to be foamed

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a physical change of state or due to chemical Decomposition. Many such agents therefore require the presence of worms in a system in order to initiate a response or change the state; it may also be necessary to have gas supplies to dispense gaseous propellants to introduce .. The properties of typical physical and chemical foaming agents are described in manuals, z.E, in Modern Plastics Encyclopedia, Volume 52, No. TOA, Verlag McGrav; -Hill 1975, pages 126 to 129. e.g. carbon dioxide, have been absorbed on the surface of activated charcoal to make plastic foams, namely by releasing the gas when heated (see US patent

2,518,454) Propellants such as carbon dioxide and refrigerants also absorbed on molecular seven. A porous, particle-shaped, solid gas carrier became liquid, organic plastics added to cause expansion of the resulting plastic system to counteract shrinkage effects, that occur during curing (see U.S. Patent No.

3 969 785). The particulate gas carrier, which is a highly porous Has structure, sets during the hardening of the plastic releases the trapped gases in a controlled manner, providing numerous small bubbles around the To compensate for shrinkage without endangering essential physical properties of the product. Among the substances mentioned there are dust coke (fluid coke), activated aluminum oxide, activated bauxite and silica gel. Such materials were various cement mixes added to successfully prevent shrinkage (see US Pat. No. 3 503 767, 3 519 449, 3 794 504, 3 890 157 and Re-26,277).

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In pending U.S. patent application Ser. No. 772 847 (1977) a composition was described and a method of making it of organic plastic frames using teilch en-shaped substances. Urethane foams can thus be produced that dust coke, which contains both gas and water, is added to a mixture of isocyanate and polyol.

The foam-making processes described in the above-referenced patents are relatively specific, either in respect of either the blowing agent or the purpose or the material being foamed. In such specific uses the general applicability of the foam process to other systems is limited and it cannot be precisely predicted whether a propellant or a process can be transferred to another system. Although a foam of a chemically modified, cross-linked polysulfides represented by sulfur using carbon dioxide as a propellant, there is a need for a composition and a method for foaming solid, liquid,

/from
These materials, for example elemental sulfur, with the help of other means than the use of conventional propellants.

Rigid foams can be made from normally solid but liquefying materials, with the limitations avoided, which are normally associated with the use of conventional propellants, which act on a change of state are based or based on a chemical reaction to produce the gas. According to the invention this is achieved by that certain selected, solid, particulate substances are added to the solid, liquefying material, either

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alone or in conjunction with conventional propellants. the solid, particulate substance acts as a carrier for an agent which acts as a propellant when the material is in the liquid state, but under normal storage conditions is not released from the solid, particulate substance. The solid, particulate matter does not suffer any physical or chemical modification to create the foaming effect.

The properties of the foam or cellular structure created by the addition of solid, particulate substances can be varied using various particles, particle sizes, quantities and methods; this can be done to a greater extent than is possible using conventional propellants alone, because the solid, particulate substance remains in the material when it hardens and gives properties that are above those which can only be achieved by foaming. Certain selected particles can, for example, also serve as conventional fillers or as additives that can be used to make physical Transferring characteristics, e.g. structural strength, surface texture, Color, insulation properties, slip resistance and the same. In comparison with conventional propellants, they are also economical.

The composition and the method according to the invention find a particularly advantageous application in the manufacture of Sulfur foams and cellular aggregates which are produced by using dust coke or anthracite coal as solid, particulate substance can be added to the molten, powdered elemental sulfur. In addition to the fixed,

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particulate matter, conventional propellants can be used. The solid, liquefying material is a material which is solid under normal conditions, but which can be liquefied by melting or by any means other device that uses heat and / or pressure or a solvent from which the material is resolidified can be recovered.

It is therefore an object of the present invention to provide a composition to provide and a process for the production of foams from solid, liquefying substances, namely using a solid, particulate substance as the initiator of the foaming effect.

Another object of the present invention is to provide a foamed, solid, liquefying material that has a reduced density and is solid, particulate Contains substance that is neither physically nor chemically consumed in the process of producing the foaming effect will.

Another object of the present invention is to provide a composition and a process for the production of sulfur foam, and the sulfur foam produced thereby, using various solid, particulate substances that cause the foaming effect, when added to the liquefying material.

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Further features and advantages of the present invention result from the following description and the exemplary embodiments. The following examples illustrate the preferred Embodiments of the present invention.

EXAMPLE 1

Fumed coke, particle size 30-325 mesh US standard screen size and taken from a supply under normal ambient conditions, was added to molten elemental sulfur powder obtained from Stauffer Chemical Company under the designation "Triangle". A measured amount of sulfur was heated in an oven at 162.8 ⁰ C and the desired quantity by weight of Staubkoks was added. The results are shown in Table 1; the table contains the weight ratios of the components; the results show that the density, expressed in pounds per cubic foot, of the sulfur after hardening decreases as the amount of dust coke increases. The decrease in density is greater than the difference in density between the two components, which proves that a foaming effect is taking place.

TABEL 1 1 2 3 4 * Attempt no. 50
0
118 50
12.5
88.2 50
25th
72 50
37.5
62.9 sulfur
Dust coke
Density, in pounds
per cubic foot

* reheated after mixing

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EXAMPLE 2

It was the same method as in Example 1 was conducted except _s, however, that the Staubkoks with the sulfur was previously mixed and heated with this at 162.8 ⁰ C. When the mixture had melted, it was removed from the furnace, wherein she froze. The results are shown in Table 2; it can be seen from them that the heating of the sulfur with solid, particulate! Dust coke as an additive leads to a lower foaming effect if larger amounts are used, so that the mixing process represents a possibility by which the properties of the sulfur foam can be varied. This means that although a greater amount of the solid particulate can be added, the overall density can still be controlled by its apparent dependence on the manner in which it is mixed with the sulfur.

TABLE 2 5 6th 7th Attempt no. 50 50 40 sulfur 12.5 25th 30th Dust coke 89.3 92.2 72.1 Density, in pounds
per cubic foot

50 85.5

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EXAMPLE 5

In this example, the same procedure was followed as in the two previous examples, with the exception, however, that the dust coke used was small in particle size, less than 100 mesh, and was made different for comparison solid, particulate material used, namely fine Anthracite charcoal, with a particle size of less than 100 mesh. The results are shown in Table 3; they show that the use of fine, solid, particulate material leads to a greater foaming effect and to a reduced density, compared to the material with a larger particle size. In addition, the use of solid, particulate anthracite charcoal creates a sulfur foam that is exactly one has such a low density or even a lower density than can be achieved with fine dust coke; this proves that too a foaming effect is produced and, in the case of the addition of larger amounts of solid, particulate substances, appears the foaming vortex to be more pronounced because the density is lower than when using a similar amount of dust coke.

TABEL 9 3 10 11 12 * 13 * Attempt no. 50 100 100 50 50 sulfur 12.5 40 - 25th - Dust coke - - 40 -. 25th Anthracite coal 59 61 48 55.4 58.2 Density, in pounds per cubic foot

* Heated for 3 minutes after mixing

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EXAMPLE 4

In this example, the particulate matter became fine Anthracite coal and regular dust coke used together with a chemical propellant, p-toluenesulfanylhydrazide, under the name "Celogen TSH" from Uniroyal, Inc. and is intended for use with rubber. The same procedure as in Example 1 was carried out, except that the samples were returned to the oven to reheat 5 to 7 minutes after mixing will. The results are shown in Table 4; they show that a chemical blowing agent continues the production reinforced with a foam, the density of the product being reduced when it solidifies.

TABEL 14th 4th 15th 16 Attempt no. sulfur 25th - - Anthracite coal - 25th 25th Dust coke 0.5 0.5 - CeI.TSH 51 62.1 70.6 Density, in pounds
per cubic foot

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EXAMPLE 5

The effectiveness of 'other solid' particulate substances was tested by the same procedure as in Example 1. The particulate substances were added to the sulfur, and

/ corresponding

although the proportions of 25 parts by weight of the particulate Make it up to 100 parts by weight of sulfur. The results for the various particulates are in the table listed; they show that the other particulates are nowhere near as effective in reducing density like dust coke and anthracite coal. This is surprising and

unexpected as some of these materials are known to be industrial adsorbents and are organic in the art should effectively foam plastic materials.

TABLE 5

Attempt no. particulate matter Density, in pounds per cubic foot 17th Silica gel 110.6 18th Clay (Clay) 108 19th plaster 111.7 20th Activated bauxite 113.8 21st Activated aluminum 123.5

oxide

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EXAMPLE 6

Particulate matter derived from those evaluated in Example 5 Substances selected were used along with the chemical blowing agents used in Example 4 to determine whether any improvement occurred? The results are shown in Table 6; they show a decrease in density, the tinting is mainly due to the propellant alone. A dense, non-absorbent, particulate substance, Ottawasand was also used for comparison.

TABLE 6

Attempt no. 22nd 23 24 sulfur 50 50 50 particulate
material Silica gel activated
bauxite Ottawa sand lot 20th 25th 35 CeI. TSH 0.5 0.5 0.5 Density, in pounds
per cubic foot 93 62.6 126.7

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EXAMPLE 7

In order to determine whether the foaming effect of the dust coke is due to moisture in the pores or on the surface of the dust coke, which evaporates as a result of the heat of fusion of the sulfur, producing gaseous vapor for foaming purposes, a series of tests were carried out in which dust coke was used that was used under normal ambient conditions, ie room temperature and normal room humidity; Mfergleichszwecken Staubkoks was used, which had been dried at 121 ⁰ G. The results are shown in Table 7; they show that the use of the dried material only led to a small increase in density, so that the foaming effect must be attributed to causes other than just the moisture content. A conventional blowing agent was also used with the dried dust coke, the results again showing that drying of the dust coke resulted in little loss of foaming action.

TABLE 7
Experiment No. 25 26 27 28

Sulfur 50 50 50 50 Dust coke - 25 - 25

Dust coke (dried 25 - 25)

CeI. TSH - - 0.5 0.5

Density, in pounds 86.9 74.7 80.4 71.8

per cubic foot

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TO EXAMPLE 8

Another solid, particulate substance, calcium carbide,

/ it was added to the molten sulfur alone and 'together with other substances to determine whether there is a foaming effect entry. As can be seen in Table 8, calcium carbide called no foaming effect itself. However, in combination with other materials that use water or moisture as a foam material introduced into the system, there was a foaming effect and also a decrease in density. In experiment no. 32 with Plaster of paris, water, bound to the plaster of paris, was added to the mixture and the mixture was! reheated after the ingredients had been mixed together "

29 TABEL 8th 31 10 - 32 10 Attempt no. 50 30th 50 69.3 50 49 sulfur 0.5 50 0.5 0.5 Calcium carbide - 0.5 - - Dust coke - 30th - volume - - plaster - Density, in pounds 52.3

per cubic foot

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EXAMPLE 9 /

Line-like, aggregate-shaped particles with a light weight
were prepared by mixing solid, particulate substances with the molten sulfur, following the procedure of Example 1 except that the resulting mixture was poured into cold water to solidify it. A low-density aggregate material was obtained which has the properties shown in Table 9 when fine dust coke of a uniform size is used.

33 TABLE 9 5 92 35 86 Attempt no. 50 34 50 sulfur ■ - 50 37.5 Dust coke 12, 25th - Dust coke (fine) 88 Density, in pounds
per cubic foot

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The examples listed show the advantageous aspects of the invention, especially when applied to the solid, liquid becoming material sulfur, namely when using different, solid, particulate substances, especially dust coke and Anthracite coal; however, other materials can be used. Paraffin wax, for example, was mixed with sulfur beforehand ^ melted and dust coke was added; the proportions were 50 parts by weight of sulfur, 10 parts by weight of wax and 25 parts by weight of dust coke, whereby a foam having a density was obtained of 78 pounds per cubic foot. A combination of walnut shells and ammonium carbonate also produced foams in sulfur. Other solid, liquefying materials, e.g. Metal systems and solid, particulate substances which cause a foaming effect in such systems can be used will. The essential criteria in such systems are that they can be mixed and at the associated temperatures a foaming effect can be generated.

The invention is particularly suitable for the use of solid, particulate substances that cause a foaming effect in the solid, liquefying material, with a reduction the density occurs; however, syndiotactic foams can also be used using sulfur as a binder. For example, preformed bubbles can be used instead of bubbles generated by the foaming action of a particulate matter. For example, sulfur was melted and then glass beads (grade 200 "Q-CeI") were added to it from Philadelphia Quartz Corporation; the weight ratios were 50 parts of sulfur and 10 or 7 | 5 parts of Q-CeI, producing syndiotactic foams,

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which had a density of 53.6 G and 56.8 pounds per cubic foot, respectively.

The results obtained are surprising and unexpected since certain selected solid, particulate substances which are added to the solid but liquefied materials, can lead to foams, which have a reduced density dec solid material during hardening and solidification. Not all solid, particulate substances work successfully and some of them that should be expected to have an effect, e.g. the so-called industrial adsorbents act only in a limited way, the surprising and the unexpected Reinforcement through the use of solid, particulate substances is obtained, e.g. dust coke and anthracite coal with elemental sulfur. A variety of foaming effects can also be obtained by using them together with conventional ones Propellants. In the present invention, a composition was made and a process for the production of foams from solid, liquid becoming materials by the addition of solid, particulate substances; the invention also relates to the foam made from it.

Rigid foams are made from normally solid but fluidizing materials by using certain selected, solid, particulate substances the solid, liquefying material either alone or in combination with conventional ones Propellants are added. The solid, particulate substance acts as a carrier for a unit called A propellant works when the material is in the liquid state located, however, not from the solid, particulate

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Substance is released under normal storage conditions. The solid, particulate substance suffers no physical or chemical change to produce a foaming effect «The properties of the foam or cellular structure, that can be generated by the addition of solid, particulate substances can be changed by Use of various particles, sizes, quantities and processes, above and beyond those achieved in order transferring additional characteristics, e.g. structural strength, surface texture, color, insulation properties, Slip resistance and the like. The composition and the method according to the invention have one particularly advantageous one Application in the production of sulfur foams and cell-like aggregates which are produced in that Dust coke or anthracite coal added as a solid, particulate substance to the molten, powdered elemental sulfur will.

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Claims (20)

28331 « Claims A process for the production of foams from solid, liquefying materials, characterized in that the solid Material liquefies .wird, a solid, particulate substance is selected that can cause a foaming effect in the liquefied material, without them thereby a physical or chemical change ei-suffers the solid, particulate substance the solid, liquefying material is added in such an amount that the material expands when it is in the liquid state, the Liquefied material foamed by expansion and that the material hardens in the expanded state to produce a solid foam. 2. The method according to claim 1, characterized in that the solid, particulate substance is the solid, becoming liquid Material is added after the solid, liquefied material has been liquefied. 3. The method according to claim 1, characterized by the step mixing the solid, liquefying material with the solid, particulate substance in the solid State. 4. The method according to claim 1, characterized in that the solid, particulate substance is selected from the group consisting of dust coke (fluid coke) and anthracite coal. - 20 - 809886/098 1 ORiÖINAL JMSPECTED 2833U2 5. The method according to claim h, characterized in that the solid, liquid becoming material is sulfur. 6. The method according to claim i, characterized in that the solid, particulate substance has a particle size finer than iOO nesh. 7. The method according to claim 1, characterized in, that a conventional propellant is added to the material, which the material in the course of a chemical Reaction expands or when there is a change of state that generates a gas. : 8. The method according to claim 1, characterized in that the solid, particulate substance has a foaming effect Generated release of gas, under the conditions in which the addition to the liquefied material takes place. 9. The method according to claim 1, characterized in that the solid, particulate substance has a foaming effect generated by the release of a chemical propellant under the conditions in which it is liquefied Material is added. 10. The method according to claim 1, characterized in that the solid, particulate substance has the foaming effect by releasing both a gas and a chemical blowing agent generated under the conditions at which they are added to the liquefied material. - 21 - 809836/0981 2-833U2 11. The method according to claim 1, characterized in that the solid, liquefied material is liquefied by heating until it melts. 12. A sulfur foam, characterized by <? He ate after Verfalirenslaim 5 is produced. 13. A composition for making a foam of a solid, liquefying material, consisting of a solid, liquefying material and a solid, particulate Substance that can create a foaming effect through the expansion of the solid, liquefying material when this is in the liquid state, without any physical or chemical change occurring. 14. The composition according to claim 13 , characterized in that the solid, particulate subs ««, .- is selected from the group consisting of dust coke (fluid coke / unü Au-.xirazitkohle. 15 · The composition according to claim Ik, characterized in that the solid, liquid becoming material is sulfur. 16. The composition according to claim 13, characterized in that that the solid, particulate substance has a size that is finer than 100 mesh. 17. The composition according to claim 13, characterized in that that it additionally contains a conventional propellant that expands the material, in the course of a chemical reaction or a change of state in which a gas is generated. - 22 - 809886/0901 18. The composition according to claim 13, characterized in that the solid, particulate substance has a foaming effect generated by the release of gas under the conditions at which it was added to the liquefied material will. 19. The composition according to claim 13, characterized _f in that the solid particulate substance is a foaming action triggers by the release of a chemical blowing agent, namely in the conditions in which it is added to the liquefied material. 20. The composition according to claim 13, characterized in that that the solid, particulate substance has a foaming effect generated both by the release of a gas and by a chemical propellant under the conditions which are added to the liquefied material. 809886/0961