KR830002618B1 - Manufacturing method of asphalt substitute - Google Patents

Abstract

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Description

Manufacturing method of asphalt substitute

1 is a viscosity curve according to the temperature change of sulfur compounds, asphalt and sulfur elements.

2 shows the stress strain curves of various compositions mixed with conventional limestone flocculants.

The present invention relates to a method for producing a sulfur compound having properties very similar to asphalt, which is used as a substitute for asphalt or portland cement by hydrocarbon reaction of sulfur elements. In one aspect of the present invention, the present invention is intended to include coating materials, road paving materials, roofing materials including shingles, and generally asphalt or portland cement, in which the composition of the present invention is used instead of asphalt or portland cement. It relates to other products containing as a main ingredient.

The use of sulfur elements has been extensively designed in the civil engineering and construction industries. Indeed, pure sulfur must be mixed with non-reactive fillers, flocculants and similar products to produce 18-30% by weight of sulfur. However, the compositions of the present invention can be used in small amounts (4-8%) with fillers, flocculants and similar products to produce usable products.

The pure sulfur element is heated to its approximate melting point, 120 ° C., and then cooled to ambient temperature to produce mo-noclinic sulfur primarily and subsequently convert to orthorhombic sulfur. On the other hand, when heating the elemental sulfur to more than 159 ℃, the melt is composed of S ₈ and polymeric sulfur equilibrium mixture. Quenching the melt gives plastic sulfur ". The mixture of polymeric sulfur and amorphous S ₈ is plastic. However, this property is rapidly lost under normal pressure and room temperature. While efforts have been made to reduce the brittleness exhibited by sulfur elements by adding additives to modify sulfur, none of the attempts have been made to produce products having the same asphalt properties as the compositions of the present invention. Many additives have been devised to modify sulfur elements, but almost all of them have been to polymerizable polysulfides or materials that react with sulfur to actually produce polymeric polysulfides. Is proposed as a modifier to reduce or prevent the bridging of sulfur elements In practice, however, the production of rubbery materials requires a large amount of polysulfide of 30 to 40%, and in practice, these modifiers are expensive, so that the product is at least somewhat competitive with asphalt. Modifiers should be used in amounts of 10% or less.

Styrene monomers have also been used as sulfur modifiers. Even in this case, a large amount of monomer is used in the range of 30 to 50%, and the resulting supercooled solution has properties similar to asphalt, but the product is unstable and becomes a powdery substance that continues to be severely malodorous if overheated or reacted for too long. Is changed.

One of the most recently developed sulfur variants is dicyclopentadiene. However, when a certain amount of dicyclopentadiene is used, for example, 5% or more, an internal reaction with sulfur occurs at a temperature of 150 ° C. or higher to form a gel-like material, and this gel-like material cannot be remelted irreversibly. Make the process impossible. For this reason, in most cases the modifier is used at less than 5%, and the resulting product is superior to sulfur elements but also has hardness and brittleness. One advantage of the present invention is that it is possible to use relatively large amounts of dicyclopentadiene, for example from 10 to 20% by weight of sulfur, without forming such a gel.

According to the present invention, the sulfur element reacts with the at least first and second hydrocarbons in a constant form. The first hydrocarbon is a highly unsaturated compound having at least two double bonds, including a large number of unsaturated moieties capable of reacting with sulfur elements. These particular hydrocarbons, when themselves react with sulfur elements, form gels in much the same way as gels are produced when reacting dicyclopentadiene with sulfur as described above. However, it also has one or more unsaturated groups capable of reacting with the sulfur element, and asphalt, which can be used as an alternative to asphalt through the forward curing process by reacting sulfur with the second hydrocarbon which can prevent the formation of the gel described above. Prepare materials with almost the same properties. As described above, given the fact that the first hydrocarbon produces a gelled material when reacted alone with sulfur, the second hydrocarbon produces a material with hardness and brittleness when reacted alone with sulfur. The result is. However, when these two hydrocarbons are reacted with sulfur, they actually produce the same material as asphalt.

The fundamental change of the sulfur element characteristic by the above-described reaction is well illustrated in FIG. In FIG. 1 showing the change in viscosity with temperature, the standard yellow viscosity curve is designated as “Sulfone element”. As is well known for a long time, as the temperature of sulfur rises above its melting point, the viscosity gradually decreases until the temperature reaches about 318 ° F., and then further increases the temperature, the viscosity of the molten sulfur is several times higher with a very small temperature increase. Soaring. FIG. 1 also shows the viscosity curves of two well known asphalt, labeled AC-10 and AC-20. In FIG. 1, the viscosity curve of the preferred modified sulfur composition of the present invention, "Sulphlex # 233" is also shown. The distinctive self-lexical viscosity curves for asphalt viscosity curves compared to the sulfur curves of sulfur elements illustrate that the properties of sulfur elements have changed almost in accordance with the present invention.

As described above, the first hydrocarbon, which co-reacts with sulfur with the second hydrocarbon, forms a gel when reacted with sulfur itself. The term "gel" as used herein refers to rubbery or brittleness at room temperature. And reheating means an irreversible material that retains its solid form and does not convert into a liquid. Examples of such highly unsaturated hydrocarbons include diolefins or triolefins containing 4 to 20 carbon atoms per molecule, such as butadiene, hexadiene, octadiene and the like. Also included here are preferred first hydrocarbons: dicyclopentadiene, methylcyclopentadiene, 1,5-cyclooctadiene, 1,5,9-cyclododecartriene, myrcene, 1,7-cyclooctadiene and Cyclodiolefins (or cyclotrees) containing from 4 to 20 carbon atoms per molecule, such as cycloolefins containing double bonds reacting with sulfur in side chains such as vinyl or aryl groups (eg 4-vinyl cyclohexene-1) Olefins). It is also possible to use aryl hydrocarbons containing two or more olefinic side chains such as divinylbenzene, diallylbenzene and the like. The amount of highly unsaturated hydrocarbons used is from 5 to 20 weight percent of sulfur, preferably from 10 to 15 weight percent. In the case of the preferred dicyclopentadiene, it is preferred to use 10 to 20 weight percent of sulfur.

Secondary hydrocarbons containing one or more unsaturated groups capable of reacting with sulfur are compounds that do not react with sulfur itself to form gels, but instead produce a material with hardness and brittleness that has material properties substantially different from asphalt. . However, this second hydrocarbon prevents gel formation when reacted with sulfur with the first hydrocarbon. Such materials include monoolefins containing 2 to 20 carbon atoms per molecule, such as butene, octene; Cyclo monoolefins containing 4 to 20 carbon atoms per molecule such as cyclopentene, cyclooctene, alpha and beta piene; There are aryl hydrocarbons and dipentenes containing olefinic side chains such as vinyl benzene, vinyl toluene, allyl benzene, allyl toluene and the like, with dipentene being preferred. This second hydrocarbon is also used at 5 to 20 weight percent of sulfur, preferably in the range of 10 to 15 percent. In addition, the total amount of the first and second hydrocarbons is in the range of 25 to 30 weight percent based on the weight of sulfur.

In some cases, mixtures of two or more first hydrocarbons may be used. It is also possible to use two or more second hydrocarbons. For example, vinyl toluene or piene in an amount of 5 to 15 percent by weight of sulfur can be added together with dicyclopentadiene and dipentene to form particularly preferred formulations.

If desired, the final product of the present invention may be mixed with other materials to improve any of its properties. For example, the color of the product of the present invention ranges from cream to pale yellowish brown, yellow, orange to dark brown. Coal tar or petroleum asphalt is added to produce a black product. Coal tar allows the final product to maintain fle-xibility, and the amount used varies widely, but it is generally found that 5-25 percent of the total sulfur-hydrocarbon reaction product is preferred. It is known that coultar and asphalt can be mixed with the products of the present invention in any proportion. This fact was expected for coultar because sulfur elements and coar tars easily mix to form a single phase material. However, asphalt did not expect this because sulfur elements and asphalt were not easily mixed to form a one phase, and the solubility of sulfur in asphalt was generally limited to about 20 percent.

According to the method for preparing the product of the present invention, the sulfur element and the hydrocarbon may be mixed together, and the mixture may be heated to a temperature sufficiently high to allow an exothermic reaction and a temperature in the range of 120 ° C to 200 ° C to initiate the reaction. Usually, the mixture only needs to be heated to a temperature of about 150 ° C. to 160 ° C., at which temperature an exothermic reaction is initiated and no further heating is necessary. In some cases, it may be necessary to cool the reaction mixture to prevent the bubbles from heating to excessively occurring temperatures and to prevent excessive loss of unreacted organic compounds when the reaction is carried out in an open vessel. In this way, after the exothermic reaction has started, the reaction is preferably maintained at a temperature of about 150 ° C to 175 ° C. Of course, when the reaction is carried out in a closed vessel, the reaction temperature can be sufficiently raised without losing unreacted organic compounds. Although reaction time changes with reaction temperature of course, generally 1 to 8 hours is enough.

Alternatively, the sulfur can be heated to molten and hydrocarbons can be added, after which the heating process is carried out as described above. If such a process is used, it is preferred to add both hydrocarbons at the same time, or to react with the addition of a second hydrocarbon and then add the first hydrocarbon, otherwise, if the primary amount of at least 5 percent of the first hydrocarbon is added, the bubbles The gelation is likely to make the introduction of the first hydrocarbon and the destruction of the gel difficult.

In some cases, it may be desirable to add a small, but sufficient amount of catalyst to the reaction mixture to facilitate the reaction. Particularly preferred catalysts are polysulfides. One particularly preferred method of catalysis is to perform the reaction simply in a vessel, by preparing a prior balch of the product of the present invention so that the residue in the vessel can serve as the necessary catalyst.

Preferred compositions of the present invention are as follows:

Each of these compositions is prepared by heating a mixture of each compound to about 150 ° C., wherein the exothermic reaction maintains the temperature of the reaction mixture without further external heating. Indeed, an external ice bath is used to prevent excessive heating of the mixture.

The composition of the present invention exhibits a viscosity-temperature curve that is nearly similar to asphalt, as shown in FIG. In addition, the composition of the present invention is characterized by a transmittance of 5 to 10 (as defined by ASTM D-5), a softening point of 10 to 70 ° C. (as defined by ASTM D-36) and a ductility of at least 100 (ASTM D-113). Regulations).

Some of the compositions of the present invention can be used to exhibit a flexible pavement form that appears with asphalt when mixed with different grades of flocculant. Other compositions of the present invention can be used to exhibit a rigid packaging form exhibited by portland cement when mixed with different grades of flocculant. Thus, the compositions of the present invention can be used in combination with different grades of flocculant to represent packages whose properties can vary from flexible packaging to rigid packaging.

The flexibility (or stiffness) range of the various compositions (6 weight percent of the composition, the remainder limestone) mixed with conventional limestone flocculents is shown here with reference to FIG. The composition of the modified sulfur binder is as follows:

In the above, S is sulfur; VT is vinyl toluene; DCPD is dicyclopentadiene; CDC is a cyclodiene dimer concentrate (a mixture of about 70% DCDP and 20% methyl DCDP with the remainder highly unsaturated hydrocarbons); St is styrene; CT is coal tar; LP-3 is a polymer having a cyclic unit -S ₄ CH ₂ CH ₂ OCH ₂ OCH ₂ CH ₄ S-.

In the field test, three different products according to the invention were made. Each is No. 230, no. 233 and No. 126. No. 230 and No. The composition of 233 is as described above, No. 126 is as follows:

Batches of these products are prepared and then transferred to standard asphalt pavement plants for use in place of conventional asphalt. The process in this plant uses the product of the invention instead of asphalt and is the same as that used for asphalt except that it is not diluted or emulsified with a solvent. About 100 tons of limestone flocculant is mixed with each product, each product being used in an amount ranging from 6 to 8 weight percent of the flocculant. The coated flocculant is paved on the road using standard asphalt pavement techniques.

The compositions of the present invention can be emulsified with water in a manner very similar to asphalt. For example, 1 part of the reaction product of 61% sulfur, 13% vinyl toluene, 13% dicyclopentadiene and 13% coul tar is mixed with 1 part by volume of water in the presence of caustic and oleic acid at 65 to 75 ° C. do. Easily emulsify by mixing the components using a high speed stirrer.

In addition to use as road pavement, other uses of the composition of the present invention are as follows:

The main advantage of the present invention is that it is a substitute for asphalt. Another advantage is that the specific gravity of the composition is 1.5 to 1.7. Unlike asphalt having a specific gravity of 1, the coating material of the present invention does not fall off from the substrate when used as a coating material in water, particularly in seawater. Another advantage is that there is solvent resistance to paradine hydrocarbons such as gasoline, diesel fuel and motor oil. Finally, a major advantage over asphalt, in particular dicyclopentadiene containing products, is that they have sef-extinguishing characteristics. A piece of product consisting of 61% sulfur, 13% vinyl toluene, 13% DCPD and 13% coul tar and a piece of AC-10 asphalt are fired with a propane torch. As soon as the torch is removed, the sulfur product begins to form charcoal on its surface and extinguish itself. In contrast, asphalt continues to burn until it is completely consumed, increasing in strength. This improved fire resistance is an excellent advantage, in particular for roofing materials.

[Example 1]

Molten sulfur 4200 at a temperature of about 160 ° C. in a steel jacket bin of 4 feet × 4 feet × 8 feet length of 900 pounds of dipentene, 675 pounds of commercial dicyclopentadiene, and 225 pounds of 95% pure dicyclopentadiene. Add to pounds. Cover the bin with a 3/4 inch plywood lid. As a catalyst, 8 pounds of polysulfide (lump of sulfrex produced in the laboratory) is added together with 4 gallons of vinyl toluene. Stir slowly.

After one night, the temperature was 130 ° C., the viscosity was 32 poise and the ductility test showed stretching above 100 cm and the softening point was 47 ° C. H ₂ S analysis resulted in 0.001% H ₂ S with the probe within 2 feet of the open container, and was not detected at greater distances.

The mixture is held at about 140 ° C. for an additional 2 days, at which point dipentaene 116 is added to reduce the viscosity to 1 poise. After one hour, about 4600 pounds or 380 gallons of the resulting product is pumped from the bin to a 1500 gallon trailer tank and transported for use in an asphalt batching plant. Here, the product is transferred into a storage tank, where 7% product, 35% crushed limestone (3/4 inch to 1/4 inch), 24% crushed limestone (size between 10 and 1/4 inch sieve), It is used as a binder for a pavement mixture containing 25% limestone dust and 9% silica sand ground through -10 sieve. The temperature of the mixture when prepared from a pug mill is about 155 ° C. and the H ₂ S meter shows approximately 0.01% H ₂ S directly above the mixture. H ₂ S could not be measured at a distance of 5 feet from the mixture.

The mixture is transferred to the place of use and poured on top of the front end loader and placed on the bottom of a small lay-down machine used to construct parking lot packaging. The mixture is packaged about 3 inches thick, 30 feet wide and 35 feet long on top of the wet subgrade. It is reciprocated twice without vibration using a small vibration roller and reciprocated twice while vibrating again. The density of the mat measured after one day was between 137 and 143 pcf, which is between 93% and 97% density measured in the laboratory using a Marshall tester.

[Examples 2 to 4]

Throughout the entire process of Example 1, the product of the present invention was successfully applied, and thus three different products were prepared and tested in a similar manner using the following mixture.

About 6,000 products were made in each example, and two bins were used to make enough of each product for the planned test. In this experiment, losses due to manufacture, transportation and mixing of the product with the flocculant are as follows for each product (two bins):

700 pounds of residue left in the bin (two bins) without being flattened = 60%

100 g of evaporation of the modifier from the tank and bin = 1%

100 pounds of residue left in conveying tank (flow tank pump) = 1%

Remaining Batch Residue in the Batch Plant 2,000 lbs = 16%

12,000 losses total £ 2,900 = 24%

All compositions are successfully handled using standard asphalt mixing plants and unloaders. No special issue was raised.

Claims (1)

5-20% by weight of a first hydrocarbon (for sulfur) selected from dicyclopentadiene, methyl cyclopentadiene, divinyl benzene, cyclooctadiene, cyclodecatrienne, octadiene and myrcene and dipentene, styrene, vinyl 5 to 20% by weight of a second hydrocarbon selected from toluene, finene and octene (relative to sulfur) is reacted at a temperature high enough to cause exothermic reaction with sulfur, i. A process for producing a substitute for asphalt or portland cement, characterized in that it produces a product having a transmittance of from 100 to 100 ° C., a softening point of 10 ° to 70 ° C., and a ductility of at least 100.

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