JPS5945627B2 - Sulfur cement composition and sulfur concrete - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to sulfur cement and sulfur concrete made from sulfur cement.

Sulfur cement has special uses, namely: sealing joints;
It has been used since ancient times as a roofing material, decorative item, etc., and as a coating material for the exposed surfaces of iron stairs.

All attempts to produce high strength, durable concrete-like materials from sulfur cement have encountered cost, durability, or other obstacles and have not reached the stage of industrialization.

To increase the strength of the sulfur binder, add coal, sand or pumice, add pitumene, metal sulfides and fibrous materials, or incorporate diesters of dithiophosphoric acid and ethylenic hydrocarbons into the molten sulfur. has been proposed.

The main reason hindering the industrialization of sulfur cement is that sulfur cement gradually becomes brittle under thermal stress and subsequently disintegrates.

This embrittlement phenomenon is thought to be caused by the gradual crystallization of initially amorphous sulfur.

Partial inhibition of crystallization was achieved with various organic or inorganic additives.

Thiokol products (polysulfide olefins) were used to stabilize the amorphous form of sulfur in sulfur cements.

However, since these cements are expensive and emit unpleasant odors, mass production has not been realized.

Although dicyclopentadiene has good stability and even favorable temperature evaporation, it imparts an unpleasant odor to sulfur cement and has other drawbacks.

For example, its vapors are extremely toxic even at low concentrations.

Furthermore, if dicyclopentadiene is used, it is necessary to reflux the dicyclopentadiene with the molten sulfur in order to avoid excessive loss of vaporous material.

It is therefore an object of the present invention to develop sulfur cement compositions which overcome the drawbacks of compositions of the existing art.

Namely, sulfur cement with excellent durability, sulfur cement which can be manufactured from subgrade sulfur, sulfur cement which is resistant to the corrosive action of salts, many acids and solvents, has good thermal insulation properties and The objective is to develop sulfur cements that can acquire high strength during the cooling period and to produce self-extinguishing sulfur concrete from these sulfur cements.

The first main feature of the present invention is that (am yellow and (b) finely divided
- To provide a sulfur cement composition consisting of a divided granular thickening agent, a binder of a surfactant solid inorganic stabilizer.

A major sub-feature of the present invention is the addition to the first main invention of a liquid organic stabilizer binder comprising up to 10% by weight of (e) an olefinic hydrocarbon polymeric material.

The polymeric material is derived from petroleum and contains about 50
Contains non-volatile content greater than % by weight, and the minimum iodine restriction by Rice method is 100c? /f? and the hydrocarbon polymer can react with sulfur to form a sulfur-containing polymer.

According to a secondary feature of the invention, the sulfur cement composition comprises:
Preferably, each 100 parts by weight of sulfur (a) stabilizer (b)
It contains about 10 to 150 parts by weight.

According to another sub-characteristic of the invention, the olefinic hydrocarbon polymer (e) is a sulfur-containing polymer formed by reaction of sulfur and olefinic hydrocarbon, preferably in a ratio of 2:1 or higher. It is a combined shape.

According to a further sub-characteristic, the particulate stabilizer, etc.) has a particle size of 1
00 mesh (0,147 mm) or less, preferably fly ash with a particle size of 200 mesh (0,074 mm) or less.

According to yet another sub-characteristic, the amount of polymer (e) is about 1-5% by weight of the total amount of sulfur.

According to yet another sub-characteristic, the main invention is modified by adding durability-imparting additives, preferably 1,5,9-cyclododecatriene, or diphenoxydithiophosphinic acid, sulfur and α-methyl. Add the reaction product with styrene.

The sulfur cement composition may be used to produce the sulfur concrete composition of the present invention.

According to a second main feature of the invention, therefore, a sulfur cement composition comprising (a) sulfur and (b) a binder of a finely divided particulate thickening surface-active solid inorganic stabilizer; B
) sulfur concrete composed of natural or artificial aggregates is provided.

According to the main sub-characteristics of the present invention, the second main invention includes:
Up to 10% by weight of (c) a liquid organic stabilizer binder consisting of an olefinic hydrocarbon polymeric material is added.

The polymeric material is derived from petroleum, contains greater than about 50% non-volatile content by weight, and has a minimum iodine constraint of 100 c? /fl, and the hydrocarbon polymer can react with sulfur to form a sulfur-containing polymer.

Preferably, the ratio of B/A in the sulfur concrete composition is such that (B) is about 20-64 and (A) is about 36-64.
It is 80.

Sulfur concrete as described above has various sub-characteristics similar to the sub-characteristics of sulfur cement as described below.

According to another sub-characteristic of the invention, the olefinic hydrocarbon polymer (C) is a sulfur-containing polymer formed by reaction of sulfur and olefinic hydrocarbon, preferably in a ratio of 2:1 or higher. It is a combined shape.

According to a further sub-characteristic, the particulate stabilizer (b) is fly ash having a particle size of less than 100 mesh, preferably less than 200 mesh.

According to yet another sub-characteristic, the amount of polymer (e) is about 1-5% by weight of the total amount of sulfur.

According to yet another sub-characteristic, the main invention is modified to include additives imparting fire resistance, preferably 1,5,9-cyclododecatriene, or diphenoxydithiophosphinic acid, sulfur and α-methyl. Add the reaction product with styrene.

The present invention provides a sulfur cement that can be used in the production of sulfur concrete, which is widely applied in the field of construction industry.

The cement of the invention overcomes the drawbacks of existing products,
It also has many obvious advantages.

The sulfur cement, which is the main feature of the present invention, uses thickening, surfactant stabilizers and, if desired, supplementary chemical stabilizers.

The proportion of chemical stabilizers can be varied according to the use of the cement.

The chemical stabilizers used in the compositions of the present invention are derived from petroleum, have a non-volatile content of greater than about 50% by weight, and have a minimum Rice Iodine Number of 100 c fl/f! It may be any olefinic hydrocarbon polymer that can react with sulfur to form a sulfur-containing polymer.

Usually, the amount of chemical stabilizer used is about 10% by weight of the total amount of sulfur.
and preferably about 1 to 5% by weight of the total amount of sulfur.

The amount of chemical stabilizer as described above depends on the use and desired properties of the cement.

Chemical stabilizers can be incorporated into the final cement mix by several means.

Preferably, the chemical stabilizer is pre-reacted with a portion of the required amount of sulfur in the final mix at about 140° C. for about 30 minutes.

The resulting concentrate may be stored for future use or dissolved into a residual amount of sulfur (liquefied) to present the required amount of sulfur in the final mix at the mixing temperature. good.

Typical chemical stabilizers include, for example, RP220, although any chemical stabilizer having the properties described above can be used.
(Trademark, Exxon Chemical Co.), R
PO20 (trademark, Exxon Chemical Co.
), CTLA (Trademark, Enjay Chemical
Co, ) and Escopol (trademark, Es5o C
chemical AB, Sweden).

Both are thermally reactive olefinic liquid hydrocarbons produced by partial polymerization of olefins.

In order to provide a sulfur-containing cement according to the first main feature of the invention having a processable consistency, finely divided thickening materials such as fly ash, gypsum, dolomite, pulverized limestone, pyrite and A mixture with pyrrhotite or the addition of rock dust is required.

These particles have a particle size of 100 mesh or less, preferably 200 mesh or less.

A product of combustion of hydrocarbon fossil fuels, usually in the form of hollow microspheres called cenospheres, containing large amounts of silicon oxide and aluminum oxide and small amounts of ferric oxide, calcium oxide, magnesium oxide, sodium oxide, and potassium oxide. Fly ash, which is composed of carbon, is a particularly effective thickening material in view of its small particle size, shape, and surface structure.

Said material is independent of the cement raw material (imparts a high degree of durability in the final cement) and serves two functions: thickener and sulfur cement stabilizer.

Depending on the fineness of the fly ash and the desired consistency, it is advantageous to add fly ash in an amount of 1 to 1.5 times the total weight of sulfur.

The salient feature of the sulfur cement, which is the main feature of the present invention, is that the sulfur cement does not require high-purity sulfur, but is manufactured using subgrade sulfur containing hydrocarbon impurities, wind dust, and other "contaminants."It's about getting.

Although it was determined that the presence of hydrogen sulfide (H2S) in sulfur was harmful, it is usually possible to remelt the sulfur using simple methods.
The concentration of this contaminant can be reduced to a harmless level.

The cement produced according to the first main feature of the invention comprises:
Resistant to the corrosive effects of salts, many acids and solvents.

However, high concentrations of thermal oxidizing acids and concentrated strong bases attack cement.

Cement is virtually impermeable to moisture, has good thermal insulation properties, can be used at high temperatures without adding water and acquires high strength during cooling.

Thus, sulfur concrete pouring operations can be carried out in cold climates without the freezing problems always associated with conventional Portland cement concrete, which requires water for curing.

There is a wide range of aggregate types that can be used with the sulfur cement, the first major feature of the present invention, to produce strong, durable concrete, the second major feature of the present invention.

Among the conventional aggregates used advantageously in this case are sand,
Crushed cinder, brick powder, foundry sand, crushed quartzite, crushed limestone, powdered silica, aerated shale, aerated clay, crushed barite,
Crushed brick, crushed Portland cement concrete and crushed granite.

Preferably, the aggregate particles are angular and have a rough surface texture formed by grinding.

Using a sufficient amount of fluid mix or using a hot formwork will accurately replicate the surface of the formwork.

In areas where sulfur is readily available, cement and concrete, which are the main features of this invention, can be produced at competitive prices.

Since sulfur cement and aggregates of various densities are compatible,
For example, from about 10 pounds per cubic foot to about 100 to 23
Concrete can be produced in a very wide range of densities, from 0 pounds per cubic foot to about 500 pounds per cubic foot.

The second main feature of the invention, sulfur concrete, can be modified using conventional methods using steel, asbestos, fiberglass or other reinforcements.

The second main feature of the invention, sulfur concrete, contains about 1 part ash by weight of sulfur and is self-extinguishing.

Furthermore, by adding suitable additives such as 1,5,9-cyclododecatriene or the reaction product of diphenoxydithiophosphinic acid with sulfur and α-methylstyrene in the manner described in U.S. Pat. No. 3,459,717, It may provide fire resistance and/or prevent the formation of S02 upon heating.

Sulfur concrete, the second main feature of the invention, made from the sulfur cement, the first main feature of the invention, is not refractory and will soften and dissolve when heated above 120°C.

However, the presence of sulfur reduces the thermal conductivity of concrete, thereby retarding the rate of dissolution.

The particle size of the aggregate used in the sulfur concrete of the present invention is:
Although essentially based on the same principles as the aggregate granularity used in conventional concrete, sulfur concrete has much greater tolerance to fineness and silt content.

Approximately 80% of the final strength of the concrete is achieved in one day.

Almost 100% of final strength is obtained after 4 days.

These sulfur concretes can be used as construction materials and applied as various precast and cast-in-place concretes.

It can be used, for example, in the production of sidewalks, stairs, parking lots, road central border fences, sewer pipes, septic tanks, piles, scaffolding, foundations, pavements, industrial tanks, ponds, swimming pools, etc.

Additionally, the hot sulfur concrete mix can be pumped and sprayed to form a water- and corrosion-resistant casing on embankments, roads, railway lines, irrigation canals, agricultural reservoir linings, and the like.

The following examples illustrate embodiments of the invention by way of example only.

Samples 1-7 Prereaction of Hydrocarbon Stabilizer The hydrocarbon stabilizer (approximately 25°C) was added to molten sulfur (approximately 140°C) with vigorous stirring.

Heat was applied to maintain the reaction temperature at about 140-150°C.

The reaction continued at this temperature for approximately 15-40 minutes.

The progress of the reaction could be checked by observing the homogeneity of the mix, carefully observing the temperature of the reaction mixture, or observing an increase in the viscosity of the mixture.

When the weight ratio of sulfur to stabilizer was less than 4:1, control of the addition rate was necessary to prevent the exothermic reaction from raising the temperature above 155°C.

At that temperature hydrogen sulfide (H2S) was evolved, which induced foaming and decomposition of the product.

When the reaction occurred under the above specified conditions, a sulfur-containing polymer was produced.

The polymer acquired glassy properties upon cooling and retained this property permanently.

The properties of the olefinic hydrocarbon polymers used for illustrative purposes are shown in Table 1.

Reaction conditions for producing seven additional sulfur-containing polymers are shown in Table 2.

Examples 1-9 Sulfur cement and concrete made from the sulfur cement The sulfur cement of the first set of Examples 1-9 contains the required amount of sulfur (minus the content in the pre-reactant) and the pre-reacted The materials were mixed together and then fried to give the desired consistency to the cement.

Then aggregate was added to produce sulfur concrete.

The mix was stirred in a + cubic foot heated concrete mixer at about 130° C. for about 15 minutes and poured into forms.

Compaction was performed by applying vibration and light tapping to the formwork.

For ease of illustration, RP220 was used as the hydrocarbon stabilizer in both examples.

Examples 10-13 A second set of sulfur cement and sulfur concrete was made in a manner similar to Examples 1-9.

These examples used untreated stabilizer (ie, not pre-reacted with sulfur), and the stabilizer was added directly to the mix instead of the pre-reactant addition of the former examples.

Stirring time was extended to 20 minutes to allow complete reaction to occur.

Reference Examples 14-22 In a third set of sulfur cement and sulfur concrete made in a similar manner to Examples 1-9, the hydrocarbon stabilizer was omitted.

Sulfur concrete produced from such mixes has limited uses.

That is, it can only be used in relatively isothermal applications, such as underground or underwater structures, where temperature change cycles are very gentle.

The results are summarized in Table 3 below.

Examples 23-25 and Reference Example 26 Sulfur cement and sulfur concrete were produced in a manner similar to Examples 1-9.

For each example, water absorption rate, change in compressive strength by weathering test under thermal stress, and presence or absence of cranking were measured.

The results are shown in Table 5.

The table also includes comparative data for sulfur concrete containing only fly ash as a binder (reference example).
.

The above test results revealed that when a chemical stabilizer is added to a sulfur cement containing sulfur and fly ash in an amount of about 10% by weight or less based on the total amount of sulfur, the water absorption rate increases (decreases).

Furthermore, it was found that the occurrence of cracking was suppressed and the compressive strength was maintained at a high level (without decreasing) in a weather test.

Claims (1)

[Claims] 1 (8) (a) sulfur; (b) derived from petroleum, containing about 50% by weight or more of non-volatile content, and having a minimum iodine restriction according to the Rice process.
00 cf/f and further reacts with sulfur to form a sulfur-containing polymer and is capable of being present as a sulfur-containing polymer in the sulfur cement; (c) for sieving purposes; a sulfur cement comprising: a thickening surface-active particulate solid inorganic stabilizer preferably comprising fly ash of a size that passes through a 0.147 mm screen; and a sulfur cement comprising: said liquid organic stabilizer for each 100 parts by weight of sulfur is about 10% by weight or less and the solid inorganic stabilizer is about 1% by weight or less.
0 to about 150 parts by weight, and (B) a natural or artificial aggregate. 2 The ratio of sulfur cement (A) to aggregate (B) is 20
~64: The sulfur concrete composition according to claim 1, characterized in that it is 80 to 36. 3. The sulfur concrete composition according to claim 1 or 2, wherein the particulate inorganic stabilizer has a size that allows it to pass through a screen with a mesh size of 0.074 mm. 4. A sulfur concrete composition according to any one of claims 1 to 3, characterized in that the liquid organic stabilizer is about 1 to 5% by weight of the total sulfur. 5 The ratio of sulfur to liquid organic stabilizer is approximately 2.45:1.
5. The sulfur concrete composition according to any one of claims 1 to 4, characterized in that the sulfur concrete composition is a dog or a dog. 6. The sulfur concrete composition according to any one of claims 1 to 5, which contains an additive to impart fire resistance. 7. The sulfur concrete composition according to claim 6, wherein the additive is 1,5,9-cyclododecatriene. 8. The sulfur concrete composition according to claim 6, wherein the additive is a reaction product of diphenoxydithiophosphinic acid, sulfur and α-methylstyrene.