KR20120096385A - Modified sulfur binder and the fabrication method thereof, hydraulic modified sulfur material composition and the fabrication method thereof or combustible modified sulfur material composition and the fabrication method thereof containing the modified sulfur binder - Google Patents

Abstract

PURPOSE: A modified sulfur binder is provided to obtain physical properties which can re-melt the modified sulfur binder at 100 °C or less by using alkylamines together with a dicyclopentadiene-based modifier. CONSTITUTION: A modified sulfur binder comprises sulfur and a modifier of the sulfur. The modified sulfur binder comprises 0.01-100.0 parts by weight of dicyclopentadiene-based modifier, 0.01-200 parts by weight of alkylamine which are melt-mixed. The dicyclopentadiene-based modifier is (a) single dicyclopentadiene, (b) a mixture in which at least one of dicyclopentadiene, cyclopentadiene, dicyclopentadiene derivative, cyclopentadiene derivative, or a mixture at least one of dipentene, vinyl toluene, styrene monomer, dicyclo pentene is added to component (a) or (b).

Description

Modified sulfur binder and its manufacturing method, hydraulic modified sulfur material composition containing the same and method for manufacturing the same or flammable modified sulfur material composition and manufacturing method thereof THEREOF OR COMBUSTIBLE MODIFIED SULFUR MATERIAL COMPOSITION AND THE FABRICATION METHOD THEREOF CONTAINING THE MODIFIED SULFUR BINDER}

The present invention relates to a modified sulfur binder and a method for producing the same, and a method for producing a modified sulfur binder containing a modified sulfur binder, and a hydraulic modified sulfur material composition and a method for producing the same. A flammable modified sulfur material composition containing a modified sulfur binder and a method for producing the same.

Normally, ordinary concrete made using Portland cement exhibits alkali and very vulnerable to acids, with much of the degradation due to chemical reactions. The most common of these is the corrosion situation caused by salting or neutralization of concrete structures. In particular, concrete structures exposed to salty environment are a major problem due to premature deterioration due to corrosion of reinforcing bars. The work for repairing and reinforcing is usually a burden in terms of work time and material cost since the work is usually carried out by stacking several layers of epoxy or glass mat for repairing.

In order to overcome the disadvantages such as weak chemical resistance and strength of ordinary concrete, modified sulfur concrete using modified sulfur as a binder (binder) instead of portland cement and mixing it with various aggregates to produce mortar or concrete. Technology has been developed. In the case of using modified sulfur binders, water cannot be used due to the nature of the modified sulfur concrete, and a molten sulfur melt is used.

However, the modified sulfur concrete is limited in its application due to freeze-thaw resistance in water, surface depression caused by temperature difference between the inside and outside of the test specimen due to rapid cooling after pouring, aggregate or form preheating problem, and fire vulnerability.

In other words, as the current technology, the modified sulfur concrete should be used only in the ground, the sea, and the water, so the scope of application is limited. Therefore, the expanded use of the sulfur material as a general construction material is difficult. It's not working.

Looking more specifically, the development of technology to apply sulfur to civil engineering and construction fields using the properties of sulfur, that is, soluble above 119, solid properties at room temperature. For example, it is used as a binder of a packaging material (US Patent No. 4290816), a building material (JP-A 55-49024), or a waste solidification material (JP-A 62-15274). This is under review.

However, with regard to the combustibility of sulfur, sulfur has a flash point of 207, a spontaneous ignition temperature of 245, and flammability, and sulfur exposed to the surface has a problem of burning easily. In addition, in terms of mechanical strength, sulfur exhibits high strength when there is no defect in a stable solid state, but in reality, when cooled and solidified from a liquid state, three types of tetragonal, monoclinic, and amorphous sulfur are mixed and mixed by cooling conditions. There is a brittleness problem that tends to be defective and brittle as the ratio changes and as time passes. Therefore, the application range of pure sulfur as a binder is very limited.

Many sulfur modifiers have been investigated to remedy this drawback.

In particular, dicyclo pentadiene (DCPD) is inexpensive, so it is economical and, together with New Uses of Sulfur-, 1978, PP. As shown in 68-77 and 1978, it is known to play a good role in mechanical strength and the like.

In addition, the use of vinyl toluene, dipentene and other olefin oligomers to improve the properties of sulfur and to use them as packaging materials, adhesive materials, waterproofing materials, etc. (Japanese Patent Publication No. 25929/1991 , Japanese Patent Publication No. 2-28529).

In addition, Japanese Patent Application Laid-Open No. 2003-277108 uses tetra hydraulic indene as a sulfur modifier, and Japanese Patent Laid-Open No. 2002-60491 uses dicyclopentadiene and tetrahydroindene as a modifier. The use of both is disclosed, and it is also practical to use asphalt and sulfur as a road pavement material.

Typically, the reaction of dicyclopentadiene with sulfur can be viewed as a kind of polymerization reaction, and the reaction mechanism associated therewith is described in US Pat. No. 4,311,826. In the production of modified sulfur, the chemical reaction involves dicyclopentadiene and sulfur reacting at the beginning of the reaction, and then the sulfur is polymerized by a radical chain reaction.

However, the subsequent reaction of dicyclopentadiene with sulfur involves a large exotherm, so that the temperature and viscosity increase, making it difficult to control the reaction, and there is a problem that the solidification is rapidly solidified at room temperature and the molding cannot be performed.

To solve this problem, U.S. Patent No. 4,311,826 discloses a technique for reacting sulfur with 20 to 40% by weight of a modifier (combination of oligomer mixtures consisting of at least trimers of dicyclopentadiene and cyclopentadiene). have. In addition, Japanese Patent Application Laid-Open No. 2-28529 and its corresponding US Pat. No. 4,391,969 are polymers reacted with sulfur and 2 to 20% by weight of a modifier (modifier containing dicyclopentadiene oligomer mixture and dicyclopentadiene). Although a modified sulfur binder is disclosed, it is required to add at least 37% by weight of the cyclopentadiene oligomer in the modifier. On the other hand, Korean Patent Laid-Open No. 2006-101878 discloses that when dicyclopentadiene alone, which is substantially free of oligomers of at least trimers of dicyclopentadiene, is used as a modifier, the amount added is controlled within 2 to 4% by weight. It has been disclosed that a modified sulfur binder can be prepared with excellent stability.

Most of the above-mentioned prior arts are melt-mixed dicyclopentadiene and oligomers with sulfur as a modifier at 120 to 160, and a modified sulfur binder, which is a reaction product, is prepared in a solid phase by cooling to 120 or less, that is, at room temperature, and then about 120 After remelting the modified sulfur binder in a special mixer maintained at a temperature of ~ 160, the preheated aggregate and other additives are temporarily mixed as soon as possible to flow into the preheated formwork (or forming mold) for cooling and solidification. Sulfur concrete, sulfur asphalt, or the like is produced, or sulfur concrete, sulfur asphalt, or the like is produced by melting and mixing all of the sulfur, the modifier, and the aggregate under a certain process condition in one step.

However, the above-described prior art regarding the modified sulfur binder has the following problems.

First, the reformed sulfur binder, which is remelted and mixed with aggregate for the production of concrete, is continuously polymerized again within the above temperature range of 120 to 160. There is a problem that occurs.

Secondly, if the melt mixing time is too short in the mixer, there is a problem that the modified sulfur binder and the aggregate are not sufficiently mixed so that the obtained material is not continuous and has no gaps or smooth surfaces.

Third, when the temperature of the molten mixture is lowered, fluidity is lowered, and thus workability is not smooth, and ultimately, the cooling mixture is rapidly solidified. In order to prevent such a phenomenon, the melt mixing time is within a range that permits physical properties of the sulfur concrete product. There is a restriction in the shortest possible time.

Meanwhile, in the art, a method of preparing a modified sulfur binder in solid form by reacting sulfur and dicyclopentadiene, and then mixing the aggregate with the aggregate to produce concrete or the like has become a technology trend.

All of the modified sulfur binders to date, or all civil and building construction materials containing them, have relatively cheap manufacturing costs compared to cement, and despite their excellent physical properties such as strength, chemical resistance and super fast stiffness, Because it has the problem of being vulnerable to fire, it must be used only in the ground, the sea, and the water, so its scope of application is limited. Therefore, it is not possible to expand the sulfur material as a general construction material. There is a situation.

Many prior patents on reformed sulfur, such as Japanese Patent Application Laid-Open No. 2003-277108 and Japanese Patent Application Laid-Open No. 2004-2113, have disclosed that the modified sulfur concrete is more stable than pure sulfur concrete by performing flame retardancy or ignition test. However, since the modified sulfur concrete is polymer concrete, when it comes into contact with a large flame source such as in the case of a fire, there is a problem that a large disaster such as earthquake disaster occurs continuously because it ignites within a short time and loses its function as a concrete structure. .

On the other hand, in order to solve the above problems, a method of mixing sulfur, heterocyclic amines and dicyclopentadiene-based modifiers has been proposed, but this also has a relatively low production rate due to the slow reaction rate and the production cost is relatively high. The problem of high and the adverse odor that occurs in the produced product has been raised.

The present invention has been made to solve these conventional problems, the object of the present invention,

1) By using alkylamines, which were not previously used as sulfur modifiers to modify sulfur, by mixing them with dicyclopentadiene-based modifiers, they exhibit the properties of remelting at temperatures below 100, the evaporation temperature of water, The present invention provides a modified sulfur binder and a method for producing the same, which can reduce manufacturing costs and have almost no adverse smell in the produced product.

2) providing a method of completely dissolving the modified sulfur binder having non-hydrophilic (hydrophobic) in water up to 100 using a surfactant,

3) the composition of the modified sulfur binder and the modified sulfur binder containing the surfactant and water to mix the aggregate and the hydraulic material (for example, hydraulic modified sulfur mortar or hydraulic modified sulfur concrete) composition that does not burn Provide a manufacturing method,

4) The present invention provides a flammable modified sulfur material composition comprising the modified sulfur binder and aggregate.

These objects can be achieved by the following configuration of the present invention.

(1) sulfur,

As the sulfur modifier, 1) 0.01-100% by weight of a dicyclo pentadiene-based modifier based on 100% by weight of sulfur, and 2) 0.01-200% by weight of alkylamine based on 100% by weight of the sulfur. A modified sulfur binder, wherein the% is melt mixed.

(2) A method for producing a modified sulfur binder, characterized by melting and mixing sulfur, a dicyclopentadiene-based modifier, and alkylamines to form a liquid modified sulfur binder.

(3) sulfur, a modified sulfur binder in which 0.01 to 100% by weight of a dicyclopentadiene-based modifier with respect to 100% by weight of sulfur and 0.01 to 200% by weight of alkylamines are melt-mixed with respect to 100% by weight of sulfur;

0.01 to 50 wt% of surfactant based on 100 wt% of the modified sulfur binder,

100 to 9900% by weight of the hydraulic material with respect to 100% by weight of the modified sulfur binder,

15 to 70 wt% of water based on 100 wt% of the modified sulfur binder and the hydraulic material,

A hydraulically modified sulfur material composition comprising 80 to 400% by weight of the aggregate based on 100% by weight of the modified sulfur binder and the hydraulic material.

(4) sulfur, a modified sulfur binder in which 0.01 to 100% by weight of a dicyclopentadiene-based modifier with respect to 100% by weight of sulfur and 0.01 to 200% by weight of alkylamines are melt-mixed with respect to 100% by weight of sulfur;

0.01 to 50 wt% of surfactant based on 100 wt% of the modified sulfur binder,

100 to 9900% by weight of the hydraulic material with respect to 100% by weight of the modified sulfur binder,

Hydraulically modified sulfur material, characterized in that it comprises an aggregate of 80 to 400% by weight based on 100% by weight of the modified sulfur binder and the hydraulic material.

(5) (A) Melt and mix sulfur, dicyclo pentadiene-type modifier, and alkylamines to prepare a liquid modified sulfur binder,

(B) cooling the liquid modified sulfur binder to obtain a solid modified sulfur binder,

(C) A hydraulically modified sulfur material composition comprising producing a hydraulically modified sulfur material composition by mixing a surfactant, a hydraulic material, water, and an aggregate while melting the solid-state modified sulfur binder at a maximum of 100. Manufacturing method.

(6) A method for producing a hydraulic-modified sulfur material, characterized by cooling the hydraulic-modified sulfur material composition produced by the method (5) above to obtain a hydraulic-modified sulfur material.

(7) sulfur, a modified sulfur binder in which 0.01-100% by weight of a dicyclopentadiene-based modifier based on 100% by weight of sulfur and 0.01-200% by weight of alkylamines are melt-mixed with respect to 100% by weight of sulfur;

Combustible modified sulfur material composition, characterized in that it comprises 80 to 400% by weight based on 100% by weight of the modified sulfur binder.

(8) (A) Melt and mix sulfur and 0.01-100 weight% of dicyclo pentadiene-type modifier with respect to 100 weight% of said sulfur, and 0.01-200 weight% of alkylamines with respect to 100 weight% of said sulfur at 120-160. To produce a liquid modified sulfur binder,

(B) Combustible modified sulfur, characterized in that to produce a liquid modified sulfur material composition by mixing the liquid-modified sulfur binder and 80 to 400% by weight of the aggregate with respect to 100% by weight of the liquid-modified sulfur binder. Method of manufacturing the material composition.

(9) (A) Melt and mix sulfur and 0.01-100 weight% of dicyclo pentadiene type modifier with respect to 100 weight% of said sulfur, and 0.01-200 weight% of alkylamines with respect to 100 weight% of said sulfur at 120-160. To produce a liquid modified sulfur binder,

(B) cooling the liquid reformed sulfur binder at a temperature of up to 120 to obtain a solid reformed sulfur binder,

(C) characterized in that the liquid modified sulfur material composition is prepared by melting the solid-state modified sulfur binder at a temperature of up to 100, and then mixing 80 to 400% by weight of the aggregate with respect to 100% by weight of the molten modified sulfur binder. Method for producing a flammable modified sulfur material composition.

(10) sulfur,

0.01 to 100% by weight of a dicyclopentadiene-based modifier with respect to 100% by weight of sulfur;

0.01 to 200% by weight of alkylamines relative to 100% by weight of sulfur;

80 to 400 wt% of aggregate based on 100 wt% of the sulfur, the dicyclopentadiene-based modifier and the alkylamines in total,

Simultaneously melt-mixing for 0.01 to 3 hours at 120 to 160 to produce a liquid modified sulfur material composition of the combustible modified sulfur material composition.

(11) A method for producing a combustible modified sulfur material, characterized by cooling the liquid modified sulfur material composition produced by the method (10) above to obtain a flammable modified sulfur material.

According to the present invention,

First, in order to reform sulfur, alkylamines, which have not been previously used as sulfur modifiers, are mixed with dicyclopentadiene-based modifiers to provide reformed sulfur binders that exhibit physical properties that can be remelted at temperatures below 100, the evaporation temperature of water. can do.

Second, a surfactant can be used to completely dissolve the modified sulfur binder having non-hydrophilic (hydrophobic) in water up to 100.

Thirdly, aggregate and hydraulic materials are mixed with the modified sulfur binder and the modified sulfur binder aqueous solution containing the surfactant and water to provide a non-burning hydraulic modified sulfur material (eg, hydraulic modified sulfur mortar or hydraulic modified sulfur concrete). can do. Therefore, in comparison with conventional modified sulfur materials, the concrete is more than equivalent level in high strength, chemical resistance, and super-speed hardness, and at the same time, it has hydraulic properties, so that concrete can be poured (mixed) at ambient temperature in the air. As it is a product that is not burned, it can be used in all areas where existing general concrete is constructed and can be used as waste immobilization material.

Fourth, by providing a combustible modified sulfur material composition comprising the modified sulfur binder and aggregate is possible to work at a relatively low temperature of about 60 ~ 85, it is possible to work even in winter, can be molded without preheating the formwork in advance. .

Fifth, compared with heterocyclic amines, the smell is relatively low after production.

Sixth, the reaction rate is improved compared to the case of using the heterocyclic amines can be shortened the production time, thereby reducing the manufacturing cost and easy to apply the process during mass production.

1 is a process diagram for producing a hydraulically modified sulfur material composition of the present invention.

Hereinafter, a preferred embodiment of the present invention will be described in detail.

In the present invention, the term "hydraulic" used in hydraulic materials, hydraulic modified sulfur material compositions, hydraulic modified sulfur mortars or hydraulic modified sulfur concrete, etc., means "cemental materials or water" in KS L 0005 (standard term in the field of hydraulic cement). As expressed in the term "chemical substance", an inorganic substance or a mixture of inorganic substances refers to a substance in which a hydrate is formed by chemical reaction with water, thereby exhibiting condensation and expression of strength, and the reaction also occurs in water. More specifically, when the hydraulic material and water are mixed with the modified sulfur binder, the reaction occurs chemically, which is cured at room temperature to express the strength, and finally, the ability to be manufactured into a very dense and hardened body.

In addition, in the present invention, the term "combustible" used in a flammable modified sulfur material composition, flammable modified sulfur mortar, flammable modified sulfur concrete, etc. means the property of burning.

In the present invention, the term "modified sulfur binder" means a liquid-modified sulfur binder in which sulfur is melted and mixed with alkylamines and a dicyclopentadiene-based modifier with sulfur to modify sulfur. It means all of the solid-state modified sulfur binder obtained by cooling the modified sulfur binder of at a temperature of 120 or less, that is to room temperature.

In the present invention, the meaning of "hydraulic modified sulfur material" can be understood as follows. Academic expression based on the manufacturing method means that the modified sulfur binder is a hydraulic material obtained by mixing and molding a surfactant, water, hydraulic material, and aggregate at 100 or less and then naturally cooling and solidifying it in the air. It may be described as collectively used materials used in the field, such as hydraulic modified sulfur mortar or hydraulic modified sulfur concrete.

In the present invention, "aggregate" used when mixing with a modified sulfur binder means fine aggregate and coarse aggregate, and only fine aggregate is used when producing modified sulfur mortar, and fine aggregate when producing modified sulfur concrete. And coarse aggregates are used together.

In the present invention, "filler" is an optional component that can be used to replace the modified sulfur binder in mortar or concrete to a certain level, and plays a role of filling the fine pores inside the modified sulfur cured body. In fact, the use of very fine materials, such as fly ash, as a filler, can lead to a poor filling effect, which can cause the hardened surface to sink.

The sulfur used in the present invention is a conventional sulfur single substance, and examples of such sulfur include natural sulfur or sulfur produced by desulfurization of petroleum or natural gas, and sulfur is heated at 120 or more, preferably 125 to 140. Molten molten sulfur can be used.

Modifiers used for sulfur reforming in the present invention are alkylamines and dicyclo pentene (DCPD) -based modifiers.

Dicyclo pentadiene-based modifiers include dicyclo pentadiene (DCPD) as a modifying component, as disclosed in Korean Patent Publication No. 10-2006-101878. This DCPD may be used alone, or at least one of cyclo pentadiene (CPD), DCPD derivative, CPD derivative (e.g. methyl cyclopentadiene (MCP), methyl dicyclo pentadiene (MDCP)) Mixtures added with may be used. Exemplary compositions of such dicyclopentadiene-based modifiers include about 65-75% by weight of DCPD, about 10-20% by weight of CPD, about 10-20% by weight of their derivatives (MCP, MDCP, etc.), and about 0.1- about 20% of other components. It may be provided at 1.5% by weight. In addition, the dicyclopentadiene-based modifier may be used in the form of mixed with an olefin compound such as dipentene, vinyl toluene, styrene monomer, dicyclo pentene. The dicyclopentadiene-based modifier has a DCPD content of about 70% by weight (referred to as "purity 70%") or more, as disclosed in Japanese Patent Application Laid-Open No. 2002-60491 and Korean Patent Publication No. 10-2005-26021. Preferably, most of the commercial items called dicyclo pentadiene can be used.

In addition, the present invention newly introduces alkylamines as modifiers. The alkylamines are methylamine, ethylamine, n-propylamine, n-butylamine, isobutyl amine, t-butylamine, n-pentylamine, cyclopentylamine, isopentylamine, n-hexylamine, cyclohexyl amine , n-octylamine, n-decylamine, 1-phenylethylamine 2-phenylethylamine, allylamine, 2-dimethyl aminoethylamine, 2-methoxyethylamine, diethylamine, di-n-propylamine , Diisopropylamine, di-n-butylamine, dicyclohexylamine, triethylamine, tetraethyltetraamine, urea and the like.

In the present invention, it is possible to prepare a liquid modified sulfur binder by using alkylamines as a sulfur modifier together with a dicyclopentadiene-based modifier. That is, the liquid-modified sulfur binder may be prepared by melting and mixing sulfur and the sulfur modifier at 120 to 160 to polymerize sulfur.

In the present invention, the addition ratio of the dicyclopentadiene-based modifier used as the sulfur modifier is 0.01 to 100% by weight, preferably 1 to 70% by weight, based on 100% by weight of sulfur, and the addition ratio of alkylamines is 100% by weight of sulfur. 0.01 to 200% by weight, preferably 0.01 to 100% by weight.

The range of addition amount of the dicyclo pentadiene-based modifier in the present invention is relatively wide compared to the existing prior patents and many reasons, because the object of the invention pursued in the present invention is different from the purpose of the prior patent.

That is, the prior patent (Japanese Patent Laid-Open No. 2002-60491) discloses that the viscosity range of 20-500 mPas is most preferable because the reaction product (modified sulfur binder) in the liquid phase after the polymerization reaction is completed is stored in a storage tank. Even during storage, since the polymerization reaction proceeds continuously within the reaction temperature range when the reaction product is prepared, it finally turns into a viscoelastic material such as rubber, which causes great damage to the reaction tank itself. In order to maintain a constant viscosity, a low viscosity range is set in order to prevent the reaction from proceeding or progress very slowly.

The range of addition amount of the dicyclopentadiene-based modifier disclosed in the prior patent is, for example, 0.01 to 30% by weight (JP-A-2004-2112), 2 to 50% by weight (JP-A-2002-60491) ), 2 to 4% by weight (Korea Patent Publication 2006-101878) and the like.

In the above patents, the dicyclopentadiene-based modifier having the addition amount range is melt-mixed at 120 to 160, and when the reaction product is in the viscosity range of 15 to 1000 mPas, it is regarded as the end point of the reaction, and the reaction is abruptly stopped. It is described.

In addition, properties such as flame retardancy and chemical resistance of the sulfur-containing material are improved mainly by increasing the amount of the dicyclopentadiene-based modifier, but the improvement effect is saturated with less than 30% by weight of use. In addition, the best strength is 0.5 to 20% by weight, the elasticity is increased to more than 20% by weight, the viscoelastic material is not easy to be crooked, the fracture easily, more than 30% by weight is significantly increased Therefore, it is described that the amount of addition of the sulfur modifier can be determined in consideration of each of these properties because the reaction control becomes difficult.

In a more specific embodiment, all prior art methods in the United States, Japan, and Canada use oligomers of at least trimers of cyclopentadiene in significant amounts (e.g., 37% by weight) and take into account the strength or workability of the final product. The ways in which the final viscosity measured at 140 is to maintain the 20-500 mPas viscosity range are described. In addition, Korean Patent Laid-Open Publication No. 2006-101878 uses dicyclone pentadiene alone when used in an amount of about 3% by weight based on the total weight of the reactants, measured by ASTM D4402 method for liquid storage for about 130 to 2 weeks. One viscosity range is said to be about 10-1000 cP, more preferably about 10-500 cP. Particularly, if it exceeds 4% by weight, it acts as a factor causing the product's super-cooling phenomenon, so as to achieve the required level of hardness, a temperature that is significantly lower than the melting point of sulfur, for example, even in a short time even at room temperature It is mentioned that limiting the amount of dicyclone pentadiene added to 2 to 4% by weight is a major technical feature because it causes a problem that a lot of time is left without actualization.

However, although the present invention produces a high viscosity liquid modified sulfur binder, it is cooled to room temperature to produce a solid modified sulfur binder, and, if necessary, a water modified sulfur material composition according to a further process may be 100 or less water. It is not necessary to limit the viscosity of the desired final product to the low viscosity range, since dissolving the solid-phase modified sulfur binder in the inside is limited, and accordingly, it is necessary to limit the addition ratio of the dicyclopentadiene-based modifier to the existing patent range. There is no.

As the proportion of dicyclopentadiene-based modifier is increased, the viscosity is continuously increased and the reaction time is shortened. This may shorten the final product manufacturing time and may be a desirable aspect in terms of efficiency of product production. The large amount of addition and the rate of addition (the rate of dropping to add dicyclopentadiene-based modifiers into the molten sulfur) cause instantaneous and explosive exothermic phenomena, making the reaction difficult to control. Finally, the addition of dicyclopentadiene-based modifiers The ratio is preferably determined by comprehensively judging both of these aspects.

Therefore, in view of such a complex aspect, the liquid modified sulfur binder according to the present invention has a final viscosity in the range of 0.01 to 100.0 Pas, preferably 0.1 to 10.0 Pas, of 140 of the reaction product obtained immediately before the end of the reaction. good. It is a very wide range of high viscosities compared to the 20-500 mPas, the final viscosity measured at 140, as set forth in the preceding patent, but is a suitable viscosity range for the purposes of the present invention described above.

The technical background for selecting the high viscosity range as described above in the present invention is that the alkylamines are the most important features of the present invention.

The reaction product of the above-mentioned high viscosity range is difficult to control the reaction in the prior art, but in the present invention, such a problem can be solved by the change in the amount of alkylamines added, the mixing order and the vaporization method.

Alkylamines used in the present invention are involved in the polymerization reaction of sulfur with a dicyclopentadiene-based modifier to exert physical properties such as reaction inhibitors or viscosity modifiers to change reaction conditions, viscosity of reaction products, cooling conditions, odor removal, etc. Causes various physical property changes.

In particular, the use of alkylamines can produce a solid-phase modified sulfur binder exhibiting physical properties that can be melted again at a temperature of 100 or less, which is the most important technical feature of the present invention.

That is, all of the final products (modified sulfur binders) presented by the prior patent method cannot exhibit physical properties that can be melted again at temperatures below 100, whereas solid modified sulfur binders prepared using alkylamines according to the present invention. It was found that remelting was possible at temperatures below 100.

It is important whether the modified sulfur binder is remeltable at temperatures below 100, as shown in the process for preparing the non-burning hydraulic modified sulfur material composition, which is the final object of the present invention, which will be presented later. When the modified sulfur binder and the hydraulic material are mixed together with water to be molded, the modified sulfur binder is melted at a temperature of 100 or less, which is the precondition for the evaporation temperature of water, and is mixed with water in a liquid state using a surfactant. This is because it can be used, but even with a small amount, it can exhibit excellent properties of the modified sulfur binder.

As a comparative example, the modified sulfur binder prepared by the method described in the prior art was physically pulverized very finely, and then remelted, and remelted at about 114. The finely pulverized powder (about 100 to 200 mesh) In the same manner as the method proposed in the present invention was added to the water of 100 or less (actually boiling water) with a surfactant, but as soon as contact with the water turned into a precipitate form instantaneously. The homogenizer was used to disperse it up to 20000 RPM.However, unlike the present method, due to the excellent crushing and dispersing performance of the homogenizer, rather than remelting, finely modified sulfur particles are accompanied by a large amount of foam. It was observed to be in a dispersed state in hot water.

In addition, the autoclave, a hydrothermal synthesizer, is used to cure the finely modified sulfur powder obtained above using a hydraulic material cement and water to produce modified sulfur cement, and then to cure the precast product in the cement industry. After charging at 150 and curing at 150, the finely dispersed modified sulfur powders in the cement were burned at 150 ° C and blackened. As described above, in the case of producing the modified sulfur cement by the prior patent method, the maximum amount of finely modified sulfur powder that can be added so as not to be carbonized was about 7% by weight and started to carbonize from about 3% by weight, exceeding 7% by weight. If you do, the whole product is showing the phenomenon of carbonization.

The test results for the physical phenomena tested in comparison with the solid phase modified sulfur binder provided in the present invention are described as follows.

That is, the hydraulically modified sulfur material composition prepared by the method of the present invention was found to be easily melted again at a temperature of 100 or less, preferably at about 60, and without using a homogenizer, a mixer (mixer) When the solid-state modified sulfur binder was left at 60 ° C and supplied with a heat source of about 60, it was confirmed that it existed as a solution rather than a dispersed state. After autoclave curing, there was no trace of carbonization. In terms of physical properties, very good test results were shown.

In particular, in relation to the change in the mixing quantity compared to the case of manufacturing mortar, the test sample manufactured by the prior patent method is present in the filler (filler) concept that is dispersed without any hydraulic action (hydration) at all On the other hand, the modified sulfur binder is melted and is present in the liquid phase when the test specimen is manufactured by the method of the present invention. However, when the modified sulfur binder is mixed with cement and water, the modified sulfur binder is mixed according to the amount of addition. The change in yield was large, and the test body surface state after pouring the test dough into the mold was observed that the test body produced by the present invention was relatively more brittle.

In the present invention, the addition amount of the alkylamines as the modifier or the reaction regulator is preferably 0.01 to 200% by weight, preferably 0.01 to 100% by weight, based on 100% by weight of sulfur. As a modifier, a significant physical effect cannot be expected, and when it exceeds 200% by weight, it is a cost increase factor and a significant physical effect cannot be expected.

In the case of preparing a liquid modified sulfur binder according to the present invention, in the melt-mixing of sulfur, a dicyclopentadiene-based modifier, and alkylamines, the mixing order of the respective components is not particularly limited. It is desirable to choose the method that best suits the physical properties of the final product.

(a) A method for producing a liquid modified sulfur binder by heating a dicyclopentadiene-based modifier with sulfur, followed by addition of alkylamines and heat treatment.

(b) A method for producing a liquid-modified sulfur binder by mixing dicyclopentadiene-based modifiers with alkylamines and then adding sulfur and heat treatment.

(c) A method of producing a liquid modified sulfur binder by heating sulfur and alkylamines, followed by adding a dicyclopentadiene-based modifier and heating.

(d) A method of producing a liquid modified sulfur binder by heating and reacting sulfur with a dicyclopentadiene-based modifier followed by cooling to prepare a solid phase reactant. The solid phase reactant is then melted again, and alkylamines are added thereto, followed by heat treatment.

The method (a) is a method of adding alkylamines while polymerizing sulfur and a dicyclopentadiene-based modifier in the order of production provided in the prior art, and the amount of addition of alkylamines is relatively low compared to other methods. In addition, maintaining the viscosity range of the reaction product at 0.01 to 10.0 Pas, preferably 0.1 to 4.0 Pas at an appropriate time to add alkylamines helps to improve the physical properties of the final product.

In the method (b), alkylamines are added as a modifier or a reaction regulator to the dicyclopentadiene-based modifier in advance before the polymerization reaction, thereby suppressing a sudden increase in viscosity of the reactants and smoothly progressing the polymerization reaction, thereby facilitating reaction control. There is an advantage to this.

The method (c) is a method in which a dicyclopentadiene-based modifier is added and heat treated after directly reacting with sulfur using alkylamines, and the present inventors have a tendency to cause a polymerization reaction even when the alkylamines are directly reacted with sulfur. Found.

The method (d) is a method of preparing a stabilized modified sulfur binder and then remelting and reacting, and stably storing and reacting in a flake form.

According to the present invention, it is preferable to vaporize alkylamines in the range of 0.01 to 100.0 Pas, preferably 0.1 to 10.0 Pas while melting and reacting sulfur and dicyclopentadiene-based modifier with alkylamines. The reasons for vaporizing the alkylamines may include ease of handling (hardness) of the reaction product, removal of odors peculiar to aromatics of the alkylamines, strength and stability of the final product, and the like.

As the reaction mixer used for the melt mixing, a known one can be used as long as mixing can be sufficiently performed, and it is preferable to use a mixer for mainly liquid stirring. If the addition amount of the alkylamines is less than about 5% by weight, a closed reactor may be used.However, if the addition amount of the alkylamines is about 5% by weight or more, the removal of the odor peculiar to the alkylamines and the final state of the cake having hardness The use of a closed stirrer is not preferred in this case, since it must be vaporized to obtain the product.

The vaporization period of the alkylamines is in the range of about 0.01 to 100.0 Pas and 0.1 to 10.0 Pas of the reaction product near the time point before and after the modified sulfur precursor (precusor) starts to form while the alkylamines are heated. Vaporization at the time of holding is very helpful in improving the physical properties of the final product. In this case, the molecular weight distribution can be easily determined by analyzing the molecular weight distribution by GPC measurement in order to more accurately determine when the modified sulfur precursor starts to be produced, but in the continuous reaction step, it is cumbersome, so it is a hockey viscometer It may be convenient to measure in real time with a model such as).

The wide range of viscosities at the appropriate time of vaporization described above is because the methods for stabilizing according to the change in the mixing order of alkylamines or the physical state of the final product are carried out under various wide conditions. That is, the change in the mixing order of the alkylamines has significantly improved the stabilization phenomenon in terms of all physical properties than when the appropriate vaporization is achieved in all three mixing procedures provided above.

All existing prior patents disclose that the reaction temperature and the reaction time at that temperature are very important reaction factors to control all the physical properties of the final product in order to produce a modified sulfur binder having good physical properties. In Japanese Laid-Open Patent Publication No. 2003-277108 and Japanese Laid-Open Patent Publication No. 2002-60491, molten sulfur does not readily denature at 125 or less even by contact mixing with a sulfur modifier, and in the temperature range of 120-135, sulfur and a sulfur modifier It is said that the polymerization reaction is slow and sudden exotherm and viscosity increase do not occur, and the temperature rises slightly and the viscosity rises, so that most of them have properties that maintain a constant viscosity. In addition, in the initial mixing process, the optimum temperature range may vary depending on the type of sulfur modifier or the amount thereof added. For example, when the blending ratio of the dicyclopentadiene-based modifier is 20% by weight or more relative to 100% by weight of sulfur. Although the reaction rate is practically obtained even at 130, it is described that it requires several hours for reaction progress to be 1 weight% or less.

The reaction temperature and reaction time in the present invention can be understood to proceed similarly to the reaction conditions described in the preceding patents, but the reaction in the present invention uses a new material called alkylamines for the first time, and therefore, a method for adding alkylamines and Depending on the timing, change in the amount of alkylamines added, vaporization conditions of alkylamines, and the like, many differences occur in viscosity, strength, stability of the final product, removal of odors peculiar to aromatics of alkylamines, and ease of handling of reaction products.

Taken together with the existing mechanisms, the results of the present results show that the reaction between dicyclone-pentadiene-based modifiers and sulfur is a kind of polymerization reaction, and melt mixing, which is a key process in the reformed sulfur manufacturing process, is molten sulfur. It is a process for obtaining the modified sulfur by polymerizing sulfur by mixing with a sulfur modifier. The sulfur reforming reaction may be classified into an initial mixing reaction step in which molten sulfur and a sulfur modifier react and generate a reformed sulfur precursor, and a polymerization reaction step in which the generated reformed sulfur precursor and molten sulfur continuously react and polymerize. In the above reaction, the reformed sulfur formation reaction is an initial mixing reaction stage showing a sudden exothermic reaction and a polymerization reaction showing an endothermic reaction, and the reformed sulfur generation system changes from an exothermic reaction to an endothermic reaction as the reaction proceeds. In addition, depending on the type of sulfur modifier or the amount of addition thereof, the calorific value and the endothermic amount and the reaction time are different, and if the temperature control is not performed correctly, the polymerization reaction may runaway and solidify.

Summarizing the results studied so far in the "sulfur-dicyclo pentadiene-based modifier-alkylamines" system used in the present invention, even when the alkylamines are reacted with sulfur alone in the "sulfur-dicyclolone-pentadiene-based modifier" system As in the case of the "sulfur-dicyclopentadiene-based modifier" system, the polymerization reaction can be confirmed, and in the initial mixing reaction step, an exothermic reaction occurs to generate a modified sulfur precursor and continuously react the polymerization reaction. As a result, the stabilization phenomenon was remarkably improved in all physical properties such as viscosity, strength, hardness and stability of the final sulfur-modified binder.

In addition, the stabilization phenomenon was remarkably improved in terms of all physical properties such as ease of handling of the reaction product, removal of odors peculiar to aromatics of the alkylamines, and stability of the final product, compared to the case where the method of vaporizing alkylamines was relatively less vaporized. The vaporization period of the alkylamines is vaporized near the time point before and after the modified sulfur precursor starts to form while heating the alkylamines, i.e., when the viscosity is maintained in the range of 0.01 to 100.0 Pas, preferably 0.01 to 100.0 Pas. This is very helpful for improving the physical properties of the final product, it has been found that the method of stabilizing according to the change of the mixing order of the alkylamines or the physical state of the final product is carried out in various wide conditions.

On the other hand, the present invention uses an alkylamine, and thus exhibits a higher exothermic temperature than the heteroamine, which means that the reaction rate is faster than the heteroamine. Therefore, the present invention can proceed the reaction at a faster rate than when using a hetero amine, thereby shortening the production time, which in turn is associated with the production cost reduction by productivity improvement. However, in the present invention, it is necessary to appropriately control the reaction temperature by using a chiller in order to control a relatively high reaction temperature.

Meanwhile, in the present invention, the modified sulfur material composition and the modified sulfur material were manufactured according to the following manufacturing processes using the liquid modified sulfur binder prepared above.

(a) Combustible modified sulfur mortar and concrete composition prepared by mixing aggregate and optionally filler without mixing water in liquid modified sulfur binder, and flammable modified sulfur mortar and concrete cooled after molding.

(b) A solid reformed sulfur binder prepared by cooling the liquid modified sulfur binder at a temperature of 120 or less, which is equal to or lower than the reaction temperature.

(c) the flammable modified sulfur mortar and concrete composition prepared by melting the solid-state modified sulfur binder obtained in (b) again below 100 and then mixing the aggregate and the filler selectively without mixing water, and then molding the same. Cooled flammable modified sulfur mortar and concrete composition.

(d) a hydraulically modified sulfur mortar and a hydraulically modified sulfur concrete composition prepared by mixing a solid-state modified sulfur binder obtained in the above (b) with a surfactant, water, a hydraulic material, and an aggregate at 100 or less, and molding and cooling the same. Hydraulic modified sulfur mortar and hydraulic modified sulfur concrete.

(e) Combustible modified sulfur mortar and combustible modified sulfur concrete composition prepared by melt-mixing sulfur with dicyclopentadiene-based modifier, alkylamines and aggregates at the same time at 120 to 160 for 0.01 to 3 hours, Flammable modified sulfur mortar and flammable modified sulfur concrete after cooling.

As shown in (b), the solid-state modified sulfur binder may be obtained by cooling the liquid-modified sulfur binder at a temperature of 120 or less, which is equal to or lower than the reaction temperature. Such cooling solidification may be performed by cooling at a temperature that can be solidified. At this time, the solidification flows into any form (or mold) and solidifies, the solid flows into a form of arbitrary shape and vibration solidification while cooling, a method of cooling and solidifying while performing assembly using an assembly device. Although the present invention is not particularly limited to the above solidification methods, for example, an apparatus such as an electric type having a drum or a slanting line or a vibrating type having a horizontal or inclined tube can be used. have.

The flammable modified sulfur refers to a modified sulfur material which is easily burned at about 130 in the same way as the modified sulfur material proposed in the prior art, and the hydraulically modified sulfur material uses a torch like a general cement mortar or concrete. It means that the material does not burn even when it is lit.

One of the final objectives of the present invention is to produce a fire-resistant hydraulic modified sulfur material composition and a hydraulic modified sulfur material, which can be prepared using the manufacturing process shown in FIG. 1.

First, sulfur, a dicyclopentadiene (DCPD) -based modifier, and alkylamines are melt mixed to prepare a liquid modified sulfur binder. According to the present invention, a stable modified sulfur binder showing physical properties equivalent to those of conventional products can be prepared by introducing alkylamines as sulfur modifiers for the first time and using them with a dicyclopentadiene-based modifier. Since the modified sulfur binder has properties that can be remelted at 100 or less, which is the evaporation temperature of water, it is possible to mix mortar or concrete at 100 or less according to a subsequent process. At this time, the dicyclo pentadiene-based modifier is mixed in the range of 0.01 to 100% by weight, preferably 1 to 70% by weight with respect to 100% by weight of sulfur, alkylamines 0.01 to 200% by weight with respect to 100% by weight of sulfur Preferably, it is preferable to mix in 0.01-100 weight% range. In addition, the melt mixing is preferably made in the temperature range of 120 ~ 160. The types of DCPD-based modifiers and alkylamines used in the present invention, the order of mixing, the reaction temperature and time, and the vaporization method of alkylamines are as described above.

The liquid reformed sulfur binder is then cooled to obtain a solid reformed sulfur binder. At this time, the cooling temperature is preferably a temperature of 120 or less that is less than the reaction temperature.

Subsequently, a surfactant, a hydraulic material, water, and an aggregate are mixed in a state in which the solid modified sulfur binder is melted at a maximum of 100 to prepare a hydraulic modified sulfur material composition. Since the modified sulfur is a flammable polymer compound that burns well, the non-burning hydraulic inorganic material is added, and since the modified sulfur binder obtained above is non-hydrophilic, a surfactant is used to mix mortar or concrete in water of 100 or less. To perform. The kind and addition ratio of the said additive substance are mentioned later.

The hydraulically modified sulfur material composition is then cooled to obtain a hydraulically modified sulfur material. In this case, the cooling may be a method of naturally cooling in the atmosphere.

In order to prepare the hydraulically modified sulfur material (mortar or concrete) composition of the present invention, a surfactant, water, hydraulic material, and aggregates are prepared by mixing a solid-state modified sulfur binder at 100 or less, in which the appropriate amount of each raw material is added. Are divided into mortar and concrete composition are shown below.

a) In the case of a hydraulically modified sulfur mortar composition, the amount of the surfactant added is in the range of 0.01 to 50% by weight, preferably in the range of 0.1 to 10% by weight with respect to 100% by weight of the modified sulfur binder, and the amount of the hydraulic material added to the modified sulfur binder. It is in the range of 100 to 9900% by weight, preferably in the range of 700 to 900% by weight with respect to 100% by weight, and the mixing ratio of water is in the range of 15 to 70% by weight with respect to 100% by weight of the combined sulfur binder and the hydraulic material. It is in the range of 25 to 50% by weight, and the blending ratio of the fine aggregate is in the range of 80 to 400% by weight, preferably in the range of 100 to 200% by weight, based on 100% by weight of the modified sulfur binder and the hydraulic material.

b) In the case of hydraulically modified sulfur concrete compositions, the amount of surfactant added is in the range of 0.01 to 50% by weight, preferably in the range of 0.1 to 10% by weight relative to 100% by weight of the modified sulfur binder, and the amount of the hydraulic material added to the modified sulfur binder. It is in the range of 100 to 9900% by weight, preferably in the range of 700 to 900% by weight with respect to 100% by weight, and the mixing ratio of water is in the range of 15 to 70% by weight with respect to 100% by weight of the combined sulfur binder and the hydraulic material. It is in the range of 25 to 50% by weight, and the mixing ratio of the aggregate is in the range of 80 to 400% by weight, preferably in the range of 100 to 200% by weight, based on 100% by weight of the modified sulfur binder and the hydraulic material. The blending ratio of the coarse aggregate is in the range of 1: 0.1 to 1: 4 by weight, preferably 1: 1 to 1: 2.5.

Examples of the surfactant include anionic surfactants such as soap and alkylbenzenesulfonate salts, cationic surfactants such as higher amine halides, quaternary ammonium salts and alkylpyridinium salts, nonionic surfactants such as nonylphenol and octylphenol, At least one of amphoteric surfactants such as amino acids can be used.

Such hydraulic materials include fly ash, ordinary portland cement as defined in KS L 5201, blast furnace slag fine powder, silica fume, blast furnace slag cement, metakaolin or cements mentioned in KS L 0005 (standard term in hydraulic cement field), sulfuric acid At least one selected from the group consisting of calcium and mixtures thereof can be used. Such hydraulic materials provide non-combustibility to hydraulically modified sulfur materials, and also act as a kind of filler to enable close filling of hydraulically modified sulfur materials and to prevent dents.

In addition, the aggregate is not particularly limited as long as it can be used as aggregate, but it is preferable to use recyclable industrial waste, and the like, such as steel sand, crushed stone, coal ash, sea sand, silica sand, gravel, silica, quartz powder, lightweight aggregate, and clay minerals. And one or two or more kinds selected from the group consisting of glass powders can be used. Most preferably, the best strength is achieved by filling the gaps with modified sulfur binders, hydraulic materials, or fillers when the aggregate is at its optimum closest fill.

Here, when the mixing ratio of the modified sulfur binder is less than about 10% by weight (when the aggregate exceeds 90% by weight), the surface of the inorganic material as the aggregate cannot be sufficiently wetted, the aggregate is exposed, and the strength is not sufficiently developed. There is a fear that the degree of ordering cannot be maintained. On the other hand, if the mixing ratio of the modified sulfur binder exceeds about 60% by weight (when the aggregate is less than 40% by weight), the properties of the modified sulfur binder alone appear and the strength tends to decrease. The amount of the modified sulfur binder added is preferably in the range of 20 to 40% by weight. Since the mixing ratio of the modified sulfur binder and aggregate varies depending on the type of aggregate, it is preferable to select appropriately from within the above range.

In addition, one or two or more selected from the group consisting of reinforcing bars, steel fibers, fibrous fillers, fibrous particles, flaky particles, and mixtures thereof as the flexural strength reinforcement is added to 100 wt% of the modified sulfur binder and the hydraulic material. It may be further included in the range of 1 to 20% by weight. In addition, one or two or more selected from the group consisting of polymer cements, polymer cement mortars, and mixtures thereof, which are conventionally used in order to maximize the application object that can be used in the present invention, modified sulfur binder and hydraulic material It may be further included in the range of 10 to 50% by weight relative to 100% by weight. Furthermore, a group consisting of a hardening accelerator, a curing retardant, a fastening agent, and a mixture thereof in order to adjust the curing time suitable for the working environment, a high-performance sensitizer for improving the fluidity during mixing, an air entrainer for improving long-term durability One or two or more selected from the group may further include in the range of 0.1 to 3% by weight based on 100% by weight of the modified sulfur binder and the hydraulic material, and a colorant (pigment) may be removed for aesthetic effect. For the purpose of the present invention, a fragrance or the like may be used in the range of 0.1 to 3% by weight based on 100% by weight of the modified sulfur binder and the hydraulic material.

The mixer which can be used when preparing the hydraulically modified sulfur mortar or concrete composition is a conventional mixer capable of temperature control in the range of -20 to 100, and the preheating temperature of the formwork (or the molding mold) is in the range of 50 to 100. It is preferable.

As described above, a liquid modified sulfur binder is prepared, and cooled to room temperature again to produce a solid modified sulfur binder, and then melted again to prepare a hydraulic modified sulfur material composition, that is, a hydraulic modified sulfur mortar and a hydraulic modified sulfur concrete composition. Prepared.

On the other hand, it will be described below with respect to the flammable modified sulfur material composition and a method for manufacturing the same, and a flammable modified sulfur material and a method for producing the cooled after forming the same.

The combustible modified sulfur material composition according to the present invention comprises the modified sulfur binder obtained above and 80 to 400% by weight of aggregate, preferably 100 to 200% by weight, based on 100% by weight of the modified sulfur binder (see FIG. 1). ).

In addition, the flammable modified sulfur material composition preferably further comprises a filler in order to optimize the filling effect, improve the fluidity and prevent depression, as a filler fly ash, ordinary portland cement prescribed in KS L 5201, blast furnace slag fine powder At least one selected from the group consisting of cements, calcium sulfate and mixtures thereof mentioned in silica fume, blast furnace slag cement, metakaolin or KS L 0005 (standard term in the field of hydraulic cement) can be used. Such filler is preferably added in the range of 1 to 80% by weight, preferably 25 to 60% by weight based on 100% by weight of the modified sulfur binder. When the amount of filler added is less than 1% by weight, the effect of closest filling is reduced, and there is a risk of sinking. When the amount of the filler is more than 80% by weight, the amount of modified sulfur binder is relatively low, resulting in lower working fluidity and lowering physical properties such as strength. May result.

When manufacturing conventional conventional modified sulfur concrete, the working temperature is about 140-160, preheats the blender and the formwork to the same temperature, and can be manufactured without the sinking phenomenon only under the closest filling operation of the filler such as fly ash. Do. In fact, in the winter outside working environment, due to the rapid cooling phenomenon outside the test body and the temperature deviation inside and outside, it was not possible to construct the site, and only the precaster product could be manufactured in the factory. However, in the case of the flammable modified sulfur material of the present invention, because the work at a relatively low temperature of about 60 ~ 85, it is possible to work even in winter, there is an advantage that can be molded without preheating the formwork in advance.

Such flammable modified sulfur material compositions can be prepared by selecting one of the following three methods.

(a)-0.01 to 100% by weight of dicyclopentadiene-based modifier with respect to sulfur, 100% by weight of sulfur, and 0.01 to 200% by weight of alkylamine based on 100% by weight of sulfur at 120 to 160 To produce modified sulfur binders,

-Flammable modified sulfur material composition, characterized in that the liquid modified sulfur material composition to prepare a liquid modified sulfur material composition by mixing up to 100 to 80% by weight of the aggregate with respect to 100% by weight of the liquid modified sulfur binder and the liquid modified sulfur binder. Method of preparation.

(b)-0.01 to 100% by weight of dicyclopentadiene-based modifier with respect to 100% by weight of sulfur, and 0.01 to 200% by weight of alkylamine based on 100% by weight of sulfur at 120 to 160 To produce modified sulfur binders,

-Cooling the liquid reformed sulfur binder at a temperature of up to 120 to obtain a solid reformed sulfur binder,

-Flammable, characterized in that the liquid-modified sulfur material composition is prepared by melting the solid-state modified sulfur binder at a temperature of up to 100, and then mixing 80 to 400% by weight of the aggregate with respect to 100% by weight of the molten modified sulfur binder. Process for the preparation of the modified sulfur material composition.

(c) sulfur;

0.01 to 100% by weight of a dicyclopentadiene-based modifier with respect to 100% by weight of sulfur;

0.01 to 200% by weight of alkylamines relative to 100% by weight of sulfur;

80 to 400 wt% of aggregate based on 100 wt% of the sulfur, the dicyclopentadiene-based modifier and the alkylamines in total,

Simultaneously melt-mixing for 0.01 to 3 hours at 120 to 160 to produce a liquid modified sulfur material composition of the combustible modified sulfur material composition.

Flammable modified sulfur material composition can be obtained by cooling the liquid modified sulfur material composition prepared by one of the methods (a), (b) and (c) above, and the flammable modified sulfur material is cooled by cooling the liquid modified sulfur material composition. As a method of obtaining a material, for example, there is a method of forming a flammable modified sulfur material by molding the liquid modified sulfur material composition in a molding mold preheated to 50 to 160, then cooling and demolding.

In the above, the present invention has been described with reference to the illustrated examples, which are merely examples, and the present invention may be embodied in various modifications and other embodiments that are obvious to those skilled in the art. Understand that you can.

Example 1 Preparation of Modified Sulfur Binder Using Triethylenetetraamine

A 500-necked 3-neck glass reactor was prepared in a thermostat (silicone oil used as a fruit) in which a constant temperature was maintained by PID (automatic temperature control). 300 g of industrial powder sulfur was introduced into the reactor to melt sulfur at about 130, and then 60 g of dicyclopentadiene (85% pure raw material of industrial purity) was gradually added in about 5 to 10 minutes while stirring the reactor impeller. At this time, stirring was performed for 60 minutes while maintaining the reaction temperature at 130 while paying attention to the sudden rise in temperature due to the exothermic reaction.

If the reaction product proceeds for 30 minutes at the time when the color becomes deep in the orange transparent state (that is, when the precursor starts to form), 30 g of triethylenetetraamine is gradually added when the reaction product turns dark red from the opaque state. To continue the reaction. As the reaction time progresses, the color becomes more intense, and at the point where the viscosity starts to occur, one trineck stopper is opened to proceed with triethylenetetraamine vaporization. As the triethylenetetraamine evaporated, almost no odor and the color turned dark black (triethylenetetraamine vaporization time 30 minutes) the final reaction temperature was 140, at which time the reaction was terminated and cooled to room temperature A modified sulfur binder was prepared.

The remelting temperature of the solid reformed sulfur binder thus prepared was about 80.

Example 2 Preparation of Hydraulic Modified Sulfur Mortar Specimens

30 g of the solid-state modified sulfur binder obtained in Example 1 and 1 g of the surfactant were mixed with water in a thermostat maintained at about 85, and then melted. Then, 300 g of Portland cement and 750 g of sand having a particle diameter of 3 to 10 mm were added thereto, using a small mixer. After mixing for about 2-3 minutes, it was molded into a five-square cubic mold, cooled in the air to prepare a hydraulic modified sulfur mortar specimen. The prepared hydraulic-modified sulfur mortar specimen was charged with a mold in a climate chamber maintained at 90% relative humidity at 23, and after 1 day was demolded from the mold to obtain a hydraulic-modified sulfur mortar specimen. The mortar test specimens were loaded into a clean tap water tank maintained by the test, and the physical properties of each mortar specimen were tested according to the course of the age.

Example 3 Preparation of Hydraulic Modified Sulfur Concrete Specimens

After mixing 28 g of the solid-state modified sulfur binder obtained in Example 1 and 1 g of the surfactant with water in a thermostat maintained at about 85, the mixture is melted, followed by 381 g of portland cement, 921 g of grain size of 3-10 mm sand, and 746 g of grain aggregate of 10-18 mm coarse aggregate. After mixing for about 2 to 3 minutes using a small mixer, it was molded into a cylindrical mold having a diameter of 10 and a length of 20 and cooled in the air to prepare a hydraulic modified sulfur concrete specimen. The hydraulically modified sulfur concrete specimen prepared was charged together with a mold in a constant temperature chamber maintained at 90% relative humidity at 23, demolded from the mold one day later, and then a hydraulically modified sulfur concrete specimen was obtained. The test was carried out to test the properties of concrete specimens with the passage of age.

Example 4 Preparation of Modified Sulfur Binder Using Butylamine

A 500-necked 3-neck glass reactor was prepared in a thermostat (silicone oil used as a fruit) in which a constant temperature was maintained by PID (automatic temperature control). 300 g of industrial powder sulfur was introduced into the reactor to melt sulfur at about 130, and then 60 g of dicyclopentadiene (85% pure raw material of industrial purity) was gradually added in about 5 to 10 minutes while stirring the reactor impeller. At this time, stirring was performed for 60 minutes while maintaining the reaction temperature at 130 while paying attention to the sudden rise in temperature due to the exothermic reaction.

If the reaction product proceeds for 30 minutes at the time when the color becomes thick in the transparent state of orange color (that is, when the precursor starts to form), the reaction is gradually added by adding 30 g of butylamine when the reaction product turns dark red from the opaque state. Continue on. As the reaction time proceeds, the color becomes more intense, and at the point where the viscosity starts to occur, one 3-neck stopper is opened to proceed with butylamine vaporization. As the butylamine evaporated, almost no odor and the color changed to dark black (butylamine vaporization time 30 minutes), the final reaction temperature was 140, at which time the reaction was terminated and cooled to room temperature to modify the solid sulfur binder Was prepared.

The remelting temperature of the solid reformed sulfur binder thus prepared was about 75.

Example 5 Preparation of Hydraulic Modified Sulfur Mortar Specimens

30 g of the solid-state modified sulfur binder obtained in Example 4 and 1 g of the surfactant were mixed with water in a thermostat maintained at about 85, and then melted. Then, 300 g of Portland cement and 750 g of sand having a particle diameter of 3 to 10 mm were added thereto, using a small mixer. After mixing for about 2-3 minutes, it was molded into a five-square cubic mold, cooled in the air to prepare a hydraulic modified sulfur mortar specimen. The prepared hydraulic-modified sulfur mortar specimen was charged with a mold in a climate chamber maintained at 90% relative humidity at 23, and after 1 day was demolded from the mold to obtain a hydraulic-modified sulfur mortar specimen. The mortar test specimens were loaded into a clean tap water tank maintained by the test, and the physical properties of each mortar specimen were tested according to the course of the age.

Example 6 Preparation of Hydraulic Modified Sulfur Concrete Specimens

After mixing 28 g of the solid-state modified sulfur binder obtained in Example 4 and 1 g of the surfactant with water in a thermostat in which about 85 is maintained, the mixture is melted, usually 381 g of Portland cement, 921 g of grain size 3-10 mm, and 746 g of coarse aggregate 10-18 mm thick. After mixing for about 2 to 3 minutes using a small mixer, it was molded into a cylindrical mold having a diameter of 10 and a length of 20 and cooled in the air to prepare a hydraulic modified sulfur concrete specimen. The hydraulically modified sulfur concrete specimen prepared was charged together with a mold in a constant temperature chamber maintained at 90% relative humidity at 23, demolded from the mold one day later, and then a hydraulically modified sulfur concrete specimen was obtained. The test was carried out to test the properties of concrete specimens with the passage of age.

Experimental Results 1. Measurement of Physical Strength

The liquid phase change of the test body according to the remelting temperature change of the solid-state modified sulfur binder obtained in Example 1 or Example 4 was compared.

In order to measure the physical properties of the specimens using the solid-state modified sulfur binder obtained in Example 1 or Example 4, the compressive strength, flexural strength and adhesion strength were measured.

Compressive strength and flexural strength were tested according to KS L ISO 679 "Cement Strength Test Method". The strength test measured the compressive and flexural strengths of the square specimens with dimensions 40mm * 0mm * 60mm. The compacted specimens are wet cured for 24 hours, then demolished and cured underwater until strength testing. When the test age was reached, the test body was taken out of the curing tank under water, the bending strength was measured, and then the compressive strength test was performed on the broken specimen. It was measured in the same manner as. The results showed that the compressive strength value similar to the case where general modified sulfur was added when the developed sulfur produced in the present invention was added. In addition, when the developed sulfur prepared in the present invention was added, the flexural strength value was superior to that of the general modified sulfur.

Adhesion strength was carried out according to the adhesion characteristics of concrete and mortar, KS F 27625 concrete repair, and test method of adhesion strength of protective materials. This test is a method of testing the adhesive strength of grout, mortar, concrete and surface protective materials for the purpose of repairing and protecting concrete structures. The test base shall be designed strength (50 ± 5) N / mm ² (maximum aggregate size 8 mm or 10). mm) was mixed with concrete according to KS F 2425 to prepare a base plate for testing according to KS F 2403. The dimensions are 50mm in height * 300mm in width * 300mm in length. After curing for 24 hours in moisture [temperature (20 ± 2) ℃, humidity above 90%], it is demolded and cured for 27 days in water (20 ± 2) ℃. It was used as. Modified sulfur mortar prepared by formulation in a test base plate was chopped into a mold and then placed on a vibrating table. Test body curing was then covered with an impervious film, demolded after 24 hours, and stored at a temperature (20 ± 2) ° C. for 27 days. In the adhesive strength test method, a tensile force (2) is applied in the vertical direction with respect to the photograph and the cut surface, and a load is applied until fracture. The load speed until the tension was broken was (0.05 ± 0.01) MPa / s.

Experimental Results 2. Deodorization Results

The odor removal of the solid phase modified sulfur binder obtained in Example 1 or Example 4 was measured using gas chromatography. The main odorous substance was the amount present in the final modified sulfur of the amine-based triethylenetetraamine or butylamine.

As a result of washing through steam during the manufacturing process, it was confirmed that the amount of detection of the amine compound in the final modified sulfur was reduced by about 30% compared with the use of pyridine, a conventional heteroamine.

Experimental results 3. Comparison of remelting temperature of modified sulfur binder

The liquid phase change of the test body according to the remelting temperature change of the solid-state modified sulfur binder obtained in Example 1 or Example 4 was compared.

After each appropriate amount of the solid-phase modified sulfur binder obtained in Example 1 or Example 4 was put into a test tube, charged into a heater controlled constant temperature, and the liquid phase change of the test piece was observed at each temperature while changing the temperature to room temperature 110-120 180 room temperature. It was.

The modified sulfur binder obtained in Example 1 or Example 4 was remelted at 85 to show a stable state without continuous phase separation even when the temperature was increased, and after cooling to room temperature, the same color and solidification as in Comparative Example 1 were obtained. The shape is shown.

Experimental results 4. Combustion test results for fires of modified sulfur mortar

A combustion test was conducted on the fire of the hydraulically modified sulfur mortar prepared in Example 2 or 5.

The shape of the specimen was observed using a hydraulic modified sulfur mortar and a general modified sulfur mortar using a torch for about 5 minutes each with a strong flame.

The hydraulic modified sulfur mortars prepared in Example 2 or 5 were not burned in the torch combustion test.

Experimental Result 5. Comparison of Mortar Surface Degradation

As a comparative test of the deterioration phenomenon of the surface of the mortar test body, the surface deterioration phenomenon which occurs when the moisture contained in the hydraulic modified sulfur mortar manufactured in Example 2 and the water contained in the portland cement mortar usually burns in a fire An experiment was made for comparison.

The surface of the hydraulically modified sulfur mortar prepared in Example 2 and the surface of the ordinary Portland cement mortar were each measured after about 5 minutes by fire using a torch for combustion.

After the torch combustion test, the surface of the hydraulic modified sulfur mortar prepared in Example 2 hardly cracked.

Claims (39)

Sulfur,
As the sulfur modifier, 1) 0.01 to 100 parts by weight of a dicyclo pentadiene-based modifier based on 100 parts by weight of the sulfur, and 2) 0.01 to 200 parts by weight of alkylamine based on 100 parts by weight of the sulfur. Modified sulfur binder, characterized in that the addition melt mixing.
The method of claim 1, wherein the dicyclo pentadiene-based modifier,
1) dicyclo pentadiene (DCPD) alone, or
2) a mixture in which at least one of cyclo pentadiene (CPD), DCPD derivative, CPD derivative is added to the DCPD, or
3) The modified sulfur binder according to 1) or 2), wherein at least one of dipentene, vinyl toluene, styrene monomer, and dicyclo pentene is added.
The modified sulfur binder according to claim 1, wherein the modified sulfur binder is in a liquid or solid phase.
A method for producing a modified sulfur binder, characterized by melting and mixing sulfur, a dicyclopentadiene-based modifier, and alkylamines to form a liquid modified sulfur binder.

According to claim 4, wherein the dicyclo pentadiene-based modifier is mixed in the range of 0.01 to 100 parts by weight based on 100 parts by weight of sulfur, and the alkylamines are mixed in the range of 0.01 to 200 parts by weight based on 100 parts by weight of sulfur. Method for producing a modified sulfur binder, characterized in that.
The method of claim 4, wherein the dicyclo pentadiene-based modifier,
1) dicyclo pentadiene (DCPD) alone, or
2) a mixture in which at least one of cyclo pentadiene (CPD), DCPD derivative, CPD derivative is added to the DCPD, or
3) A method for producing a modified sulfur binder, wherein 1) or 2) is a mixture in which at least one of dipentene, vinyl toluene, styrene monomer, and dicyclo pentene is added. .
5. The method of claim 4, wherein the melt mixing is performed in a temperature range of 120 to 160. 6.
The method for producing a modified sulfur binder according to claim 4, wherein the alkylamines are vaporized in a range of 0.01-100.0 Pas of the reaction product by melt mixing.
The method of claim 4, wherein the melt mixing is terminated when the viscosity at 140 of the reaction product by melt mixing is in the range of 0.01 to 100.0 Pas.
The method for producing a reformed sulfur binder according to claim 4, wherein the sulfur is heated with the dicyclopentadiene-based modifier, and the alkylamines are added and heated to prepare a liquid modified sulfur binder.
The method for producing a modified sulfur binder according to claim 10, wherein when the viscosity of the reaction product of the sulfur and the dicyclopentadiene-based modifier is in the range of 0.01 to 10.0 Pas, the alkylamines are added.
The method for producing a modified sulfur binder according to claim 4, wherein after mixing the dicyclopentadiene-based modifier and the alkylamines, the sulfur is added and heated to prepare a liquid modified sulfur binder.
The method for producing a reformed sulfur binder according to claim 4, wherein the sulfur and the alkylamines are subjected to a heat reaction, followed by addition and heat treatment of the dicyclopentadiene-based modifier to produce a liquid modified sulfur binder.
The liquid reformed sulfur binder according to claim 4, wherein the sulfur is reacted with the dicyclopentadiene-based modifier by heating, followed by cooling to prepare a solid phase reactant. After melting the solid phase reactant, the alkylamines are added and heat treated to form a liquid-modified sulfur binder. Method for producing a modified sulfur binder, characterized in that for producing a.
5. The method of claim 4, wherein the liquid modified sulfur binder is cooled at a temperature of up to 120 to obtain a solid modified sulfur binder.
Sulfur, 0.01 to 100 parts by weight of a dicyclopentadiene-based modifier with respect to 100 parts by weight of sulfur, a modified sulfur binder in which 0.01 to 200 parts by weight of alkylamine is melt-mixed with respect to 100 parts by weight of sulfur;
0.01 to 50 parts by weight of surfactant based on 100 parts by weight of the modified sulfur binder,
100 to 9900 parts by weight of a hydraulic material, based on 100 parts by weight of the modified sulfur binder,
15 to 70 parts by weight of water, based on 100 parts by weight of the modified sulfur binder and the hydraulic material,
A hydraulically modified sulfur material composition comprising 80 to 400 parts by weight of aggregates based on 100 parts by weight of the modified sulfur binder and the hydraulic material.
The method of claim 16, wherein the dicyclo pentadiene-based modifier,
1) dicyclo pentadiene (DCPD) alone, or
2) a mixture in which at least one of cyclo pentadiene (CPD), DCPD derivative, CPD derivative is added to the DCPD, or
3) A hydraulically modified sulfur material composition according to 1) or 2), wherein at least one of dipentene, vinyl toluene, styrene monomer, and dicyclo pentene is added.
The method of claim 16, wherein the surfactant is an anionic surfactant of at least one of soap and alkylbenzenesulfonate, a cationic surfactant of at least one of a higher amine halide, a quaternary ammonium salt and an alkylpyridinium salt, nonylphenol and octyl A hydraulically modified sulfur material composition, characterized in that at least one of at least one nonionic surfactant of phenol and an amphoteric surfactant of amino acids.
The method of claim 16, wherein the hydraulic material,
1) fly ash, or
2) ordinary portland cement, blast furnace slag fine powder, silica fume, blast furnace slag cement or metakaolin as defined in KS L 5201 (standard terminology for hydraulic cements); or
3) A hydraulically modified sulfur material composition, characterized in that it is any one selected from the group consisting of cements, calcium sulfate and mixtures thereof mentioned in KS L 0005 (standard term in the field of hydraulic cement).
The method of claim 16, wherein the aggregate is at least one selected from the group consisting of recyclable industrial waste, steel sand, crushed stone, coal ash, sea sand, silica sand, gravel, silica, quartz powder, lightweight aggregate, clay mineral and glass powder. Hydraulic-modified sulfur material composition, characterized in that.
17. The hydraulically modified sulfur material composition according to claim 16, wherein the aggregate is fine aggregate and the hydraulically modified sulfur material is hydraulically modified sulfur mortar.
The method of claim 16, wherein the aggregate comprises fine aggregate and coarse aggregate, the mixing ratio of the fine aggregate and coarse aggregate is in the weight ratio of 1: 1 to 1: 4 range, the hydraulic modified sulfur material is hydraulic modified sulfur A hydraulically modified sulfur material composition, characterized in that it is concrete.
The method according to claim 16, wherein the hydraulic modified sulfur material composition, based on 100 parts by weight of the modified sulfur binder and the hydraulic material,
1) 1 to 20 parts by weight of rebar, steel fibers, fibrous fillers, fibrous particles, flaky particles and mixtures thereof as flexural strength reinforcing materials,
2) 10 to 50 parts by weight of polymer cements, polymer cement mortars and mixtures thereof,
3) high performance water reducing agent 0.1 ~ 3 parts by weight,
4) 0.1-3 parts by weight of air entrainer,
5) 0.1 to 3 parts by weight of a curing accelerator, a curing retardant, a fastener and mixtures thereof
6) 0.1 to 3 parts by weight of colorant,
7) A hydraulically modified sulfur material composition further comprising at least one of 0.1 to 3 parts by weight of fragrance.
Sulfur, 0.01 to 100 parts by weight of a dicyclopentadiene-based modifier with respect to 100 parts by weight of sulfur, a modified sulfur binder in which 0.01 to 200 parts by weight of alkylamine is melt-mixed with respect to 100 parts by weight of sulfur;
0.01 to 50 parts by weight of surfactant based on 100 parts by weight of the modified sulfur binder,
100 to 9900 parts by weight of a hydraulic material, based on 100 parts by weight of the modified sulfur binder,
Hydraulic reformed sulfur material, characterized in that it comprises 80 to 400 parts by weight of the aggregate with respect to 100 parts by weight of the modified sulfur binder and the hydraulic material.
(A) melt-mixing sulfur, a dicyclo pentadiene-based modifier, and alkylamines to prepare a liquid modified sulfur binder,
(B) cooling the liquid modified sulfur binder to obtain a solid modified sulfur binder,
(C) A hydraulically modified sulfur material composition comprising producing a hydraulically modified sulfur material composition by mixing a surfactant, a hydraulic material, water, and an aggregate while melting the solid-state modified sulfur binder at a maximum of 100. Manufacturing method.
The method of claim 25, wherein the dicyclo pentadiene-based modifier is mixed in the range of 0.01 to 100 parts by weight based on 100 parts by weight of the sulfur, and the alkylamines are mixed in the range of 0.01 to 200 parts by weight based on 100 parts by weight of the sulfur. A method for producing a hydraulically modified sulfur material composition, characterized by the above-mentioned.
The method of claim 25, wherein the dicyclo pentadiene-based modifier,
1) dicyclo pentadiene (DCPD) alone, or
2) a mixture in which at least one of cyclo pentadiene (CPD), DCPD derivative, CPD derivative is added to the DCPD, or
3) A hydraulically modified sulfur material composition according to 1) or 2), wherein at least one of dipentene, vinyl toluene, styrene monomer, and dicyclo pentene is added. Manufacturing method.
26. The method of claim 25, wherein the melt mixing is in a temperature range of 120 to 160.
The method for producing a hydraulically modified sulfur material composition according to claim 25, wherein the liquid modified sulfur binder is cooled at a temperature of up to 120 to obtain a solid modified sulfur binder.
The method according to claim 25, wherein the surfactant is mixed in the range of 0.01 to 50 parts by weight based on 100 parts by weight of the solid-state modified sulfur binder,
The hydraulic material is mixed in the range of 100 to 9900 parts by weight based on 100 parts by weight of the solid phase modified sulfur binder,
The water is mixed in the range of 15 to 70 parts by weight based on 100 parts by weight of the solid reformed sulfur binder and the hydraulic material,
The aggregate is a method for producing a hydraulically modified sulfur material composition, characterized in that mixing in the range of 80 to 400 parts by weight based on 100 parts by weight of the solid-state modified sulfur binder and the hydraulic material combined.
A method for producing a hydraulically modified sulfur material, comprising cooling the hydraulically modified sulfur material composition produced by the method of claim 25 to obtain a hydraulically modified sulfur material.
32. The method of manufacturing a hydraulically modified sulfur material according to claim 31, wherein the hydraulically modified sulfur material composition is molded in a molding mold preheated to 50 to 160, cooled and demolded to obtain a hydraulically modified sulfur material.
Sulfur, 0.01 to 100 parts by weight of a dicyclopentadiene-based modifier with respect to 100 parts by weight of sulfur, a modified sulfur binder in which 0.01 to 200 parts by weight of alkylamine is melt-mixed with respect to 100 parts by weight of sulfur;
Combustible modified sulfur material composition, characterized in that it comprises 80 to 400 parts by weight based on 100 parts by weight of the modified sulfur binder.
34. The method according to claim 33, wherein the combustible modified sulfur material composition further comprises 1 to 80 parts by weight of a filler with respect to 100 parts by weight of the modified sulfur binder, wherein the filler is
1) fly ash, or
2) ordinary portland cement, blast furnace slag fine powder, silica fume, blast furnace slag cement or metakaolin as specified in KS L 5201; or
3) Combustible modified sulfur material composition, characterized in that any one selected from the group consisting of cements, calcium sulfate and mixtures thereof mentioned in KS L 0005 (standard term in the field of hydraulic cement).
(A) Sulfur, 0.01 to 100 parts by weight of a dicyclopentadiene-based modifier with respect to 100 parts by weight of the sulfur, and 0.01 to 200 parts by weight of alkylamine based on 100 parts by weight of sulfur at 120 to 160 Preparing a liquid modified sulfur binder,
(B) Combustible modified sulfur material, characterized in that the liquid modified sulfur material composition is prepared by mixing 80 to 400 parts by weight of the aggregate with respect to 100 parts by weight of the liquid modified sulfur binder and 100 parts by weight of the liquid modified sulfur binder. Method of Preparation of the Composition.
(A) Sulfur, 0.01 to 100 parts by weight of a dicyclopentadiene-based modifier with respect to 100 parts by weight of the sulfur, and 0.01 to 200 parts by weight of alkylamine based on 100 parts by weight of sulfur at 120 to 160 Preparing a liquid modified sulfur binder,
(B) cooling the liquid reformed sulfur binder at a temperature of up to 120 to obtain a solid reformed sulfur binder,
(C) After the solid-state modified sulfur binder is melted at a temperature of up to 100, 80 to 400 parts by weight of the aggregate is mixed with respect to 100 parts by weight of the molten modified sulfur binder to prepare a liquid modified sulfur material composition Process for producing flammable modified sulfur material composition.
Sulfur,
0.01 to 100 parts by weight of a dicyclopentadiene-based modifier with respect to 100 parts by weight of sulfur,
0.01 to 200 parts by weight of alkylamines based on 100 parts by weight of sulfur;
80-400 parts by weight of aggregate based on 100 parts by weight of the total sulfur, the dicyclopentadiene-based modifier and the alkylamines in total,
Simultaneously melt-mixing for 0.01 to 3 hours at 120 to 160 to produce a liquid modified sulfur material composition of the combustible modified sulfur material composition.
A method for producing a combustible modified sulfur material, characterized by cooling the liquid modified sulfur material composition produced by the method of any one of claims 35 to 37 to obtain a combustible modified sulfur material.
The method for producing a combustible modified sulfur material according to claim 38, wherein the liquid modified sulfur material composition is molded in a molding mold preheated to 50 to 160, cooled, and demolded to obtain a combustible modified sulfur material.

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