KR20110052556A - 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 exhibit properties capable of remelting at a temperature of 100 °C or less by modifiying sulfur by mixing heterocyclic amines or alkylamines as a modifier of sulfur with a dicyclopentadiene-based modifier. CONSTITUTION: A modified sulfur binder includes sulfur and, as a modifier of sulfur, (a) 0.1~100.0 parts by weight of dicyclo pentadiene-bsaed modifier based on 100 parts by weight of sulfur, and (b) 0.01~200 parts by weight of heterocyclic amines based on 100 parts by weight of sulfur. The heterocyclic amines are at least one selected from the group consisting of pyridine, quinoline, isoquinoline, acridine, pyrrole, piperazine, pyrolidone, their homologue, isomer of pyridine, and isomer of a homologue of pyridine.

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 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. In general, construction for renovation and reinforcement is burdened in terms of work time and material cost because the construction is usually carried out by laminating several layers of epoxy or reinforcing glass mat.

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 resistance to freeze-thawing in water, surface depression due to 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 the civil engineering and construction fields using the properties of sulfur, that is, soluble above 119 ℃ and solid 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 respect to the combustibility of sulfur, sulfur has a flash point of 207 ° C., a spontaneous ignition temperature of 245 ° C., and flammability. 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 use range of pure sulfur as a binder is very limited.

Many sulfur modifiers have been investigated to remedy this drawback.

In particular, since dicyclo pentadiene (DCPD) is inexpensive, it is excellent in economic efficiency, and together with "New Uses of Sulfur-II, 1978, PP." 68-77, 1978 ", is known to have a good effect on mechanical strength and the like.

In addition, the use of vinyl toluene, dipentene, and other olefin oligomers to improve the properties of sulfur and use it as a packaging material, adhesive material, waterproofing material, etc. (JP-A-2-25929) Japanese Patent Application Laid-Open No. 2-28529) is also known.

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 U.S. Patent 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, which is substantially free of oligomers of at least 3 dimers of dicyclopentadiene, is used as a modifier alone, the amount of addition 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 art are prepared by melting and mixing dicyclopentadiene and oligomers with sulfur as a modifier at 120 to 160 DEG C, a modified sulfur binder which is a reaction product obtained by cooling to 120 DEG C or lower, i. After remelting the modified sulfur binder in a special mixer maintained at a temperature of about 120 to 160 ° C., the preheated aggregate and other additives are mixed as soon as possible and flowed into the preheated formwork (or forming mold) as soon as possible. Sulfur concrete or sulfur asphalt is produced by solidifying or manufacturing sulfur concrete or sulfur asphalt, or by melting and mixing all of sulfur, modifier, and aggregate under specific process conditions in one step.

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

First, when the modified sulfur binder, which is remelted and mixed with aggregate to perform concrete production, is polymerized continuously again within the aforementioned temperature range of 120 to 160 ° C., the viscosity increases and eventually workability is not smooth. 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 materials containing them, have relatively low manufacturing costs compared to cement, yet have very good physical properties such as strength, chemical resistance and super fast stiffness. Because it has the problem of being vulnerable to fire and should be used only in the ground, the sea, and the water, the scope of application is limited. Therefore, it is not possible to expand the sulfur material as a general construction material. It's happening.

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. .

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

1) A mixture of heterocyclic compounds or alkylamines, which were not previously used as sulfur modifiers to modify sulfur, is mixed with a dicyclopentadiene-based modifier to exhibit physical properties that can be remelted at temperatures below 100 ° C. Providing a modified sulfur binder and a method of making the same,

2) providing a method of completely dissolving the modified sulfur binder having non-hydrophilic (hydrophobic) in water up to 100 ° C. 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) 0.1-100% by weight of a dicyclo pentadiene-based modifier with respect to 100% by weight of sulfur and 2) heterocyclic amines with respect to 100% by weight of sulfur. A modified sulfur binder, characterized in that 0.01 to 200% by weight of alkylamines are melt mixed.

(2) A method for producing a modified sulfur binder, wherein the sulfur, the dicyclopentadiene-based modifier, and heterocyclic amines or alkylamines are melt mixed to produce a liquid modified sulfur binder.

(3) Sulfur, modified sulfur in which 0.1-100% by weight of a dicyclopentadiene-based modifier based on 100% by weight of sulfur and 0.01-200% by weight of heterocyclic amines or alkylamines are melt-mixed with respect to 100% by weight of sulfur. With binders,

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 with respect to 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, modified sulfur in which 0.1-100% by weight of a dicyclopentadiene-based modifier with respect to 100% by weight of sulfur and 0.01-200% by weight of heterocyclic amines or alkylamines are melt-mixed with respect to 100% by weight of sulfur. With binders,

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,

A hydraulically modified sulfur material, characterized in that it comprises 80 to 400% by weight of the aggregate relative to 100% by weight of the modified sulfur binder and the hydraulic material.

(5) (A) Melt and mix sulfur, dicyclo pentadiene-type modifier, heterocyclic amines or 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 ° C. Method of preparation.

(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, modified sulfur in which 0.1-100% by weight of a dicyclopentadiene-based modifier based on 100% by weight of sulfur and 0.01-200% by weight of heterocyclic amines or alkylamines are melt-mixed with respect to 100% by weight of sulfur. With binders,

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) 120-200 weight% of heterocyclic amines or alkylamines with respect to sulfur and 0.1-100 weight% of a dicyclo pentadiene-type modifier with respect to 100 weight% of said sulfur, and 100 weight% of said sulfur. Melt mixing at 160 ℃ to prepare a liquid modified sulfur binder,

(B) 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 at a maximum temperature of 100 ° C. to produce a liquid modified sulfur material composition. Method for producing sulfur material composition.

(9) (A) 120-200 weight% of heterocyclic amines or alkylamines with respect to sulfur and 0.1-100 weight% of dicyclo pentadiene-type modifiers with respect to 100 weight% of said sulfur, and 100 weight% of said sulfur. Melt mixing at 160 ℃ to prepare a liquid modified sulfur binder,

(B) cooling the liquid modified sulfur binder at a temperature of up to 120 ° C. to obtain a solid modified sulfur binder,

(C) melting the solid reformed sulfur binder at a temperature of up to 100 ° C., and then mixing 80 to 400 wt% of the aggregate with respect to 100 wt% of the molten modified sulfur binder to prepare a liquid reformed sulfur material composition. The manufacturing method of the flammable modified sulfur material composition to make.

(10) sulfur,

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

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

80 to 400 wt% of aggregate based on 100 wt% of all of the sulfur, the dicyclopentadiene-based modifier, and the heterocyclic amines or alkylamines,

A method for producing a combustible modified sulfur material composition, characterized in that the liquid-modified sulfur material composition is prepared by melt mixing at 120-160 ° C. for 0.01 to 3 hours.

(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 invention,

* First, heterocyclic amines or alkylamines, which have not been used as sulfur modifiers in the past, are mixed with dicyclopentadiene-based modifiers to exhibit re-melting properties at temperatures below 100 ° C, the evaporation temperature of water. It can provide a modified sulfur binder.

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

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 can be operated 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 have.

1 is a process diagram for producing a hydraulically modified sulfur material composition of the present invention,
2A and 2B are photographs showing remelting and liquid phase changes according to temperature changes of the conventional modified sulfur binder obtained from Comparative Example 1 and the modified sulfur binder of the present invention obtained from Example 4;
3 is a photograph showing a conventional liquid sulfur binder obtained from Comparative Example 1 and the modified sulfur binder according to the present invention obtained from Example 5 in the liquid phase change according to the reaction with water in the molten state,
4 is a photograph showing the results of torch combustion experiments of the conventional modified sulfur mortar obtained from Comparative Example 2 and the modified sulfur mortar of the present invention obtained from Example 6;
5 is a photograph showing a comparison of the surface degradation phenomenon after the torch combustion test of the conventional ordinary portland cement mortar and modified sulfur mortar of the present invention obtained from Example 7.

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 melt-mixed with heterocyclic amines or alkylamines and a dicyclopentadiene-based modifier with sulfur to modify sulfur. And the solid-state modified sulfur binder obtained by cooling the liquid modified sulfur binder at a temperature of 120 ° C. or lower, 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 ° C. or lower, and then cooling it in air and solidifying it. It can be described as collectively used materials used in the field of civil engineering, for example, 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. The molten sulfur heated and melted at can be used.

Modifiers used for sulfur modification in the present invention are heterocyclic amines or 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 0.1-20% 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 introduced heterocyclic amines or alkylamines as modifiers. The heterocyclic amines include pyridine, homopyridine, isomers of pyridine, isomers of pyridine, quinoline, isoquinoline, acridine, apyridine or pyrrole. One or two or more of these may be used. Pyridine is present in large quantities along with its homologues, picoline and lutidine, via coultar, industrially and heterocyclic compounds made from such homologues pyridine base. Cyclic compound, a colorless malodorous liquid, having a molecular weight of 79.10, a melting point of -42 ° C, a boiling point of 115.5 ° C, and a specific gravity of 0.9779 (25 ° C), the derivatives of which are synthesized by synthesis. derivatives) include various pyridine carboxylic acids, pyridine sulfonic acids, pyridine aldehydes and the like. Picoline, which has almost the same physical properties as pyridine, is also called methyl pyridine, and there are three isomers (2-methylpyridine, 3-methylpyridine and 4-methylpyridine) depending on the position of the methyl group. There are six kinds of isomers such as (2,3), (2,4), (2,5), (2,6), (3,4), (3,5). However, the heterocyclic amines used in the present invention are not limited to the above listed materials.

In the present invention, a heterocyclic amine or an alkylamine may be used together with a dicyclopentadiene-based modifier as a sulfur modifier to prepare a liquid modified sulfur binder. That is, a liquid modified sulfur binder may be prepared by melting and mixing sulfur and the sulfur modifier at 120 to 160 ° C. to polymerize sulfur.

The addition ratio of the dicyclopentadiene-based modifier used as the sulfur modifier in the present invention is 0.1 to 100% by weight, preferably 1 to 70% by weight with respect to 100% by weight of sulfur, and the addition ratio of heterocyclic amines or alkylamines is It is 0.01-200 weight% with respect to 100 weight% of sulfur, Preferably it is 0.01-100 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 art (Japanese Patent Laid-Open No. 2002-60491) discloses that the viscosity range of 20-500 mPa? S 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 if it is being stored in the storage tank, the polymerization reaction proceeds continuously within the reaction temperature range at the time of preparing the reaction product, and eventually turns into a viscoelastic material such as rubber, which causes great damage to the reaction tank itself. In order to maintain stable and constant viscosity, the low viscosity range is set to prevent the reaction from progressing or to proceed 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, when the reaction product falls within the viscosity range of 15 to 1000 mPa · s by melt-mixing a dicyclopentadiene-based modifier having the addition amount at 120 to 160 ° C., the reaction is swiftly reacted. It is described as stopping.

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, becomes viscoelastic material, the molding is not easy to be skewed easily breakage, 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 ° C. is to maintain a viscosity range of 20-500 mPa · s are described. In addition, in Korean Patent Laid-Open Publication No. 2006-101878, when the amount of dicyclone pentadiene alone is used at a level of about 3% by weight based on the total weight of the reactants, the method of ASTM D4402 is stored in a liquid state at about 130 ° C. for 2 weeks. The measured 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 as a major technical feature to limit the amount of dicyclone pentadiene added to 2 to 4% by weight because it causes a problem that a lot of time is left without actualization.

However, the present invention, although a high viscosity liquid modified sulfur binder is produced to produce it as a solid modified sulfur binder by cooling it at room temperature, and if necessary to produce a hydraulically modified sulfur material composition according to additional processes of less than 100 ℃ Since dissolving the solid modified sulfur binder in water is a major technical feature, it is not necessary to limit the viscosity of the desired final product to the low viscosity range, thereby limiting the addition ratio of the dicyclopentadiene-based modifier to the extent of the existing patent range. There is no need.

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 at 140 ° C. of the reaction product obtained immediately before the end of the reaction, in the range of 0.01 to 100.0 Pa.s, preferably 0.1 to 10.0 Pa. It is good that it is a range. Although it is a very wide range of high viscosity compared with the final viscosity measured at 140 degreeC proposed by the prior patent 20-500 mPa-s, it is a suitable viscosity range for the objective of this invention mentioned above.

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

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 addition of heterocyclic amines or alkylamines, the mixing order and the vaporization method.

Heterocyclic amines or alkylamines used in the present invention are involved in the polymerization reaction of sulfur with a dicyclopentadiene-based modifier to exhibit physical properties such as reaction inhibitors or viscosity modifiers to change reaction conditions, viscosity of reaction products, and cooling conditions. It causes various physical property changes such as odor removal.

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

That is, all the final products (modified sulfur binders) presented by the prior patent method cannot exhibit the physical properties that can be melted again at a temperature of 100 ° C. or lower, whereas they are prepared using heterocyclic amines or alkylamines according to the present invention. It has been found that the solid modified sulfur binder can be remelted at temperatures below 100 ° C.

It is important whether the reformed sulfur binder is remeltable at temperatures below 100 ° C., as shown in the process for preparing the incombustible hydraulically modified sulfur material composition, which is the final object of the present invention, which will be presented later. In order to prepare the composition, the modified sulfur binder and the hydraulic material must be mixed together with water to be molded. The precondition is that the modified sulfur binder is melted at 100 ° C or lower, which is the evaporation temperature of water, and the surfactant is melted to form water and water in a liquid state. It must be able to mix together, but it can exhibit the characteristics of the excellent modified sulfur binder even in small amounts.

As a comparative example, the modified sulfur binder prepared by the method disclosed in the prior art was physically pulverized very finely and then subjected to a remelting test to be remelted at about 114 ° C., and the finely pulverized powder (about 100 to 200 mesh ) Was added to the water (actually boiling water) below 100 ℃ in the same manner as the method proposed in the present invention with a surfactant, but immediately changed to a precipitate form upon contact with water. 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 to 150 ℃ and curing, the finely dispersed modified sulfur powder in the cement was burned at 150 ℃ to find a black carbonization phenomenon. 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 ° C. or lower, preferably about 60 ° C., and without using a homogenizer, When the solid-state modified sulfur binder was left in a mixer and supplied with a heat source of about 60 ° C., it was confirmed that it existed in a solution state rather than in a dispersed state. After autoclave curing, there was no trace of carbonization. It showed very good test results in terms of overall physical properties such as.

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 heterocyclic amines or alkylamines as a modifier or a reaction regulator is preferably 0.01 to 200% by weight, preferably 0.01 to 100% by weight, based on 100% by weight of sulfur. In the case of a modifier or a reaction control agent, a significant physical effect cannot be expected, and when it exceeds 200% by weight, it can be expected to be a cost raising factor and a considerable physical effect can be expected.

97 In the case of producing a liquid modified sulfur binder according to the present invention, in the melt-mixing of sulfur, a dicyclopentadiene-based modifier, and heterocyclic amines or alkylamines, the mixing order of the respective components is not particularly limited. From among the following methods, it is preferable to select the method most suitable for the physical properties of the final product.

(a) A method for producing a liquid-modified sulfur binder by subjecting sulfur to a dicyclopentadiene-based modifier by heat reaction, and then adding heterocyclic amines or alkylamines to heat treatment.

(b) A method for producing a liquid modified sulfur binder by mixing dicyclopentadiene-based modifiers with heterocyclic amines or alkylamines, followed by adding sulfur and heating.

(c) A method for producing a liquid-modified sulfur binder by subjecting sulfur to heterocyclic amines or alkylamines by heating, followed by addition of a dicyclopentadiene-based modifier and heat treatment.

(d) Sulfur dicyclopentadiene-based modifier is reacted with sulfur, followed by cooling to prepare a solid phase reactant. The solid phase reactant is further melted, and heterocyclic amines or alkylamines are added thereto, followed by heat treatment to prepare a liquid modified sulfur binder. How to.

The method (a) is a method of adding heterocyclic amines or alkylamines by polymerizing sulfur and dicyclopentadiene-based modifier in the order of production provided in the prior art, and relatively heterocyclic amines compared to other methods. Or the amount of addition of alkylamines is low, and the viscosity of the reaction product at the appropriate time to add heterocyclic amines or alkylamines is maintained at 0.01 to 10.0 Pa.s, preferably 0.1 to 4.0 Pa.s. It helps to improve the physical properties of the product.

Since the method (b) adds a heterocyclic amine or an alkylamine as a modifier or a reaction regulator to a dicyclopentadiene-based modifier in advance before the polymerization reaction, it suppresses a sudden increase in the viscosity of the reactant and proceeds smoothly because the progress of the polymerization reaction proceeds smoothly. There is an advantage that can facilitate the control.

The method (c) is a method of directly reacting with sulfur using heterocyclic amines or alkylamines, followed by addition of dicyclopentadiene-based modifiers and heat treatment, and the present inventors have substantially combined heterocyclic amines or alkylamines with sulfur. It was found that the polymerization reaction occurred even when directly reacted.

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, while the sulfur and the dicyclo pentadiene-based modifier is reacted by melt-mixing with heterocyclic amines or alkylamines, the heterocyclic ring in the viscosity of 0.01 to 100.0 Pa s, preferably 0.1 to 10.0 Pa s It is preferable to vaporize amines or alkylamines. The reasons for vaporizing the heterocyclic amines or the alkylamines include the ease of handling (hardness) of the reaction product, the removal of the aromatic odors of the heterocyclic amines or the alkylamines, the 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 heterocyclic amines or alkylamines is less than about 5% by weight, a closed reactor may be used. However, when the addition amount of heterocyclic amines or alkylamines is about 5% by weight or more, the odor peculiar to heterocyclic amines or alkylamines The use of a closed stirrer is not preferred in this case as it has to be vaporized for removal and to obtain a cake-like final product with hardness.

The time of vaporization of the heterocyclic amines or alkylamines is near the time before and after the start of the formation of the modified sulfur precursor while heating the heterocyclic amines or alkylamines, that is, the viscosity of the reaction product by melt mixing is 0.01. Vaporization at the time of maintaining the range of -100.0 Pa.s and 0.1-10.0 Pa.s. is very helpful for 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 heterocyclic amines or 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 heterocyclic amines or alkylamines was significantly improved in all physical properties than in the case where proper vaporization was achieved in all of the 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 Unexamined Patent Publication No. 2003-277108 or Japanese Unexamined Patent Publication No. 2002-60491, sulfur in a molten state is not easily denatured at temperatures of 125 ° C. or lower even when contacted and mixed with a sulfur modifier, and sulfur and sulfur modifiers in a temperature range of 120-135 ° C. The polymerization reaction with is late and sudden exotherm and viscosity increase do not occur, and there is a tendency of maintaining a constant viscosity mostly due to slight temperature rise and viscosity rise. 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 degreeC, it is described that it requires several hours to advance reaction in the case of 1 weight% or less.

It can be understood that the reaction temperature and reaction time in the present invention proceed similarly to the reaction conditions described in the preceding patents, but the reaction in the present invention uses a new material such as heterocyclic amines or alkylamines for the first time. Viscosity, strength, stability of the final product according to the method and timing of the addition of amines or alkylamines, the amount of addition of heterocyclic amines or alkylamines, the vaporization conditions of heterocyclic amines or alkylamines, and the like. Many differences occur in the removal of odors and the ease of handling of the 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-heterocyclic amines or alkylamines" system used in the present invention, it is possible to react heterosulfur amines or alkylamines alone with sulfur. As in the Clonpentadiene-based modifier "system, the polymerization reaction can be confirmed, and as in the" Sulfur-dicyclopentadiene-based modifier "system, an exothermic reaction occurs in the initial mixing reaction step, so that the modified sulfur precursor is generated. The production and continuous reaction resulted in a polymerization reaction, which markedly improved stabilization in all physical properties such as viscosity, strength, hardness and stability of the final product, the modified sulfur binder.

In addition, the method of vaporizing heterocyclic amines or alkylamines in terms of all physical properties, such as ease of handling of the reaction product, removal of aromatic odors of heterocyclic amines or alkylamines, and stability of the final product than in the case of relatively no vaporization The stabilization phenomenon was remarkably improved, and the vaporization period of the heterocyclic amines or alkylamines was near the time before and after the start of the formation of the modified sulfur precursor while heating the heterocyclic amines or alkylamines, that is, the viscosity was 0.01 to 100.0 Pa. Vaporization at the time of maintaining the s range, preferably 0.01 to 100.0 Pa s, is very helpful for improving the physical properties of the final product, such as changing the mixing order of heterocyclic amines or alkylamines or physical properties of the final product. There are various ways to stabilize depending on the state. It turned out to be done under conditions.

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-phase modified sulfur binder prepared by cooling the liquid modified sulfur binder at a temperature of 120 ° C. or lower which is equal to or lower than the reaction temperature.

(c) flammable modified sulfur mortar and concrete composition prepared by melting the solid modified sulfur binder obtained in (b) again below 100 ° C. and mixing the aggregate and the filler selectively without mixing water, and molding the same. After-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 surfactant, water, a hydraulic material, and an aggregate at 100 ° C. or lower with the solid modified sulfur binder obtained in the above (b), and molding and cooling the same. A hydraulically modified sulfur mortar and a hydraulically modified sulfur concrete.

(e) Combustible modified sulfur mortar and combustible modified sulfur concrete composition prepared by melting and mixing sulfur with dicyclopentadiene-based modifier, heterocyclic amines or alkylamines together with aggregate at 0.01 to 3 hours at 120 to 160 ° C. And a flammable modified sulfur mortar and a flammable modified sulfur concrete cooled after forming the same.

The solid-state modified sulfur binder may be obtained by cooling the liquid-modified sulfur binder at a temperature of 120 ° C. or lower, which is below the reaction temperature, as shown in the above (b). 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 ° C. in the same way as the modified sulfur material proposed in the prior art, and the hydraulically modified sulfur material uses a torch like 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 heterocyclic amines or alkylamines (eg, pyridine) are melt mixed to prepare a liquid modified sulfur binder. According to the present invention, heterocyclic amines or alkylamines may be introduced as a sulfur modifier for the first time, and thus, a modified modified sulfur binder having a physical property equivalent to or higher than that of a conventional product may be prepared by using a dicyclopentadiene-based modifier. Since the modified sulfur binder has properties that can be remelted at 100 ° C. or lower, which is the evaporation temperature of water, it is possible to mix mortar or concrete at 100 ° C. or lower depending on a subsequent process. At this time, the dicyclo pentadiene-based modifier is mixed in the range of 0.1 to 100% by weight, preferably 1 to 70% by weight with respect to 100% by weight of sulfur, and the heterocyclic amines or alkylamines are 0.01 to 100% by weight of sulfur. It is preferred to mix in the range of 200% by weight, preferably 0.01 to 100% by weight. Moreover, it is preferable that the said melt mixing is made in the temperature range of 120-160 degreeC. The kind of DCPD-based modifier used in the present invention, heterocyclic amines or alkylamines, mixing order, reaction temperature and time, and vaporization method of heterocyclic amines or alkylamines are as described above.

The liquid reformed sulfur binder is then cooled to obtain a solid reformed sulfur binder. At this time, a cooling temperature of 120 degrees C or less which is below a reaction temperature is suitable.

126 Then, a surfactant, a hydraulic material, water, and an aggregate are mixed in a state where the solid modified sulfur binder is melted at a maximum of 100 ° C. 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 the modified sulfur binder obtained above is non-hydrophilic. Therefore, a surfactant is used to mix mortar or concrete in water below 100 ° C. Do this. 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 the solid-state modified sulfur binder at 100 ° C. or lower, and an appropriate amount of each raw material added is added. The range is shown below, divided into mortar and concrete composition.

a) In the case of hydraulically modified sulfur mortar compositions, 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 proportion of 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.

The above-mentioned surfactants include anionic surfactants such as soap and alkylbenzenesulfonate salts, cationic surfactants such as higher amine halides, quaternary ammonium salts and alkylpyridinium salts, and nonionic surfactants such as nonylphenol and octylphenol. And 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 relative to. 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 for the aesthetic effect, a colorant (pigment) is added to remove odors. For the purpose, 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 uses a conventional mixer capable of temperature control in the range of -20 to 100 ° C, and the preheating temperature of the formwork (or the molding mold) is in the range of 50 to 100 ° C. It is preferable to set it as.

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 fillers are preferably added in the range of 1 to 80% by weight, preferably 25 to 60% by weight, relative to 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 a conventional general modified sulfur concrete, the working temperature is about 140 ~ 160 ℃, preheating the blender and the formwork to be used at the same temperature, the production does not occur only under the close filling operation of the filler such as fly ash It is possible. In fact, in the winter outside working environment, due to the rapid cooling phenomenon outside the test body and internal and external temperature variations, it was not possible to construct the site, and it was possible to manufacture only precaster products in the factory. However, in the case of the flammable modified sulfur material of the present invention, because it works at a relatively low temperature of about 60 to 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) 120 to 160 ° C of sulfur, 0.01 to 200% by weight of a dicyclopentadiene-based modifier based on 100% by weight of sulfur, and 0.01 to 200% by weight of heterocyclic amines or alkylamines relative to 100% by weight of sulfur; Melt-blended to prepare a liquid modified sulfur binder,

-Flammable modified sulfur material, characterized in that the liquid modified sulfur material composition is prepared by mixing 80 to 400% by weight of the aggregate with respect to 100% by weight of the liquid modified sulfur binder and 100% by weight of the liquid modified sulfur binder. Method of Preparation of the Composition.

(b) 120-160 of sulfur, 0.01-200% by weight of dicyclopentadiene-based modifier with respect to 100% by weight of sulfur and 0.01-200% by weight of heterocyclic amines or alkylamines with respect to 100% by weight of sulfur. Melt mixing at ℃ to prepare a liquid modified sulfur binder,

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

Melting the solid modified sulfur binder at a temperature of up to 100 ° C., and then mixing 80 to 400 wt% of the aggregate with respect to 100 wt% of the molten modified sulfur binder to prepare a liquid modified sulfur material composition. Process for producing flammable modified sulfur material composition.

(c) sulfur;

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

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

80 to 400 wt% of aggregate based on 100 wt% of all of the sulfur, the dicyclopentadiene-based modifier, and the heterocyclic amines or alkylamines,

A method for producing a combustible modified sulfur material composition, characterized in that the liquid-modified sulfur material composition is prepared by melt mixing at 120-160 ° C. for 0.01 to 3 hours.

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, the liquid modified sulfur material composition is molded in a molding mold preheated to 50 to 160 ° C, cooled and demolded to obtain a flammable modified sulfur material.

Hereinafter, examples and comparative examples will be described in detail with reference to the drawings, but these examples and comparative examples are only presented to more clearly understand the present invention, and are provided for the purpose of limiting the scope of the present invention. Rather, the present invention will be defined within the scope of the technical spirit of the following claims.

Example  1. Preparation of Modified Sulfur Binder in Solid Phase

A 500-necked 3-neck glass reactor was prepared in a thermostatic chamber (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 added to the reactor. After melting sulfur at 占 폚, 60 gr of dicyclopentadiene (85% pure industrial raw material) was slowly added while stirring the reactor impeller within about 5 to 10 minutes. At this time, stirring was performed for 40 minutes while maintaining the reaction temperature at 136 ℃ while paying attention to the sudden rise in temperature due to the exothermic reaction.

When the reaction product proceeds for 10 to 20 minutes at the time when the color becomes dark in the transparent state of orange color (that is, when the precursor starts to form), slowly add 30 gr of pyridine when it turns into dark red in the opaque state. To continue the reaction. As the reaction time proceeds, the color becomes darker and the pyridine vaporization process is performed by opening one 3-neck stopper when the viscosity starts to develop. As the pyridine gradually evaporated, the smell disappeared and the color changed to dark black (pyridine vaporization time was 30 minutes), and the final reaction temperature was 140 ° C. At this time, the reaction was terminated and cooled at room temperature to obtain a solid-phase modified sulfur binder. Prepared.

The remelting temperature of the solid phase modified sulfur binder thus prepared was about 85 ° C.

Example  2. Hydraulic  Reformed Sulfur Mortar Specimen  Produce

After mixing 30 gr of the solid-state modified sulfur binder obtained in Example 1 and 1 gr of the surfactant with water in a thermostat maintained at about 85 ° C., usually 270 gr of Portland cement and 300 gr of particle diameter of 3-10 mm were added thereto. After mixing for 2-3 minutes by hand using a cutlery, molded into a 5 cm square cubic mold and cooled in the air Reformed sulfur Mortar specimens were produced. The prepared hydraulic modified sulfur mortar specimen was charged together with the mold in a constant temperature chamber maintained at 90% relative humidity at 23 ° C., and then demolded from the mold after 1 day to obtain a hydraulic modified sulfur mortar specimen. It was charged into a clean tap water tank maintained at 23 ℃, and the physical property test of each mortar specimen with the passage of age.

Example  3. Hydraulic  Modified sulfur concrete Specimen  Produce

30 gr of the solid reformed sulfur binder obtained in Example 1 and 1 gr of the surfactant are mixed with water in a thermostat maintained at about 85 ° C. and melted, followed by ordinary portland cement of 270 gr, particle diameter of 3-10 mm sand and 300 gr of particle size. 300 gr of 10-18 mm coarse aggregate was added and mixed for about 2-3 minutes by hand using a cutlery, and then molded into a cylindrical mold having a diameter of 10 cm and a length of 20 cm and cooled in the air to prepare hydraulic modified sulfur concrete specimens. Produced. 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 ° C., and then demolded from the mold after 1 day to obtain a hydraulically modified sulfur concrete specimen. It was charged into a clean tap water tank maintained at 23 ℃, and the physical properties of each concrete specimen were tested according to the age of the age.

Comparative example  1. Preparation of General Modified Sulfur Binders

In order to compare with Example 1, three holes for 6,000 ml (the center hole is equipped with a 45/50 joint) in a thermostat (silicon oil is used as a fruit) in which a constant temperature is maintained by PID method. A German IKA impeller was installed, the other hole was fitted with a condenser for a 24/40 joint, and the other hole consisted of an oligomer and a hole for DCPD). After adding 4,000 g of industrial powder sulfur, 100 cc of cyclopentadiene oligomer was added within about 5 to 10 minutes while gradually melting the liquid at 130 ° C. while gradually raising the temperature. Subsequently, after about 10 minutes, DCPD 100 ㏄ was added thereto, and stirring was performed while maintaining the reaction temperature at 140 ° C., noting that the liquid temperature rose from 130 ° C. to about 145 ° C. by the exothermic reaction. . After about 4 hours, a slight viscosity occurs. At this time, the reaction is terminated and cooled at room temperature to obtain a general modified sulfur binder.

Comparative example  2. General Modified Sulfur Mortar Specimen  Produce

The mixing ratio of the solid-state modified sulfur binder and the general sand obtained in Comparative Example 1 was mixed at a weight ratio of 1: 2, charged into a mixer maintained at about 140 ° C., melt mixed, and 5 cm preheated at about 140 ° C. General modified sulfur mortar specimens were produced by molding into square molds and cooling in air.

Comparative example  3. Common Modified Sulfur Concrete Specimen  Produce

The solid sulfur-modified sulfur: general sand: coarse sand obtained in Comparative Example 1 was mixed at a weight ratio of 1: 2: 2 in a weight ratio of about 140 ° C, and mixed in a mixer maintained at about 140 ° C. A preformed 10 cm diameter, 20 cm long cylindrical mold was molded and cooled in air to produce a general modified sulfur concrete specimen.

Experimental Results 1.Remelting Temperature Comparison 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 and the general modified sulfur binder obtained in Comparative Example 1 was compared.

An appropriate amount of the solid-phase modified sulfur binder obtained in Example 1 and the appropriate amount of the general modified sulfur binder obtained in Comparative Example 1 were put into a test tube, and then charged into a heater in which the constant temperature was controlled, followed by temperature from room temperature to 110 to 120 ° C. to 180 ° C. to room temperature. The change in the liquid phase of the test piece was observed at each temperature while the results are shown in FIGS. 2A and 2B.

As shown in Figure 2a and 2b, the modified sulfur binder obtained in Example 1 is remelted at 85 ℃ to show a stable state without continuous phase separation even when the temperature rises, after cooling to room temperature Comparative Example The same color and solid shape as in 1 are shown. On the other hand, the general modified sulfur binder obtained in Comparative Example 1 has not yet remelted at 85 ° C., is in a solid state, and it can be seen that the molten material is 110 to 120 ° C. as the temperature is continuously increased. , Cooling to room temperature shows the same color and shape as the modified sulfur binder of Example 1.

As apparent from the above experimental results, the modified sulfur binder of the present invention is melted again at 100 ° C. or lower, whereas the general modified sulfur binder is not melted at 100 ° C. or lower but melts at 110 to 120 ° C., and thus, a general modified sulfur binder is used. It was found that it was not possible to perform the operation of mixing the hydraulic material with the aggregate by remelting with a surfactant in water of 100 ° C. or less, which is a feature of the present invention.

Experimental Results 2. Comparison of Hydrophilicity of Modified Sulfur Binder with Water

The experiment for comparing the hydrophilicity of the solid-state modified sulfur binder obtained in Example 1 with the water in the molten state of the general modified sulfur binder obtained in Comparative Example 1 was carried out.

An appropriate amount of the solid-phase modified sulfur binder obtained in Example 1 and an appropriate amount of the general modified sulfur binder obtained in Comparative Example 1 were each charged into a three-necked flask, and the test pieces were melted while gradually raising the temperature. At this time, the test piece of Example 1 was melted at about 85 ° C. and the comparative example 1 at about 114 ° C., and the change of the melt was observed while slowly dropping water maintained at about 90 ° C. in each of the melted test piece melts. , The results of this 3 is shown.

As shown in FIG. 3, the modified sulfur binder of Example 1 is present in the liquid phase in a molten state without any change without any precipitate even when contacted with water at 90 ° C. in the molten state, and the modified sulfur binder of Comparative Example 1 Since the remelting temperature is 110-120 ℃, it can be seen that a precipitate immediately occurs when it comes into contact with water at 90 ℃ .Since the temperature is continuously raised, the precipitate does not melt and exists in a solid state. I could find the phenomenon going up.

Experimental results 3. Combustion test results for fires of modified sulfur mortar

The fire test of the hydraulic modified sulfur mortar prepared in Example 2 and the general modified sulfur mortar prepared in Comparative Example 2 was carried out.

The hydromorphic sulfur modified mortar and the general modified sulfur mortar were burned for about 5 minutes using a torch for combustion, and the shape of the specimen was observed. The results are shown in FIG. 4.

As shown in FIG. 4, the hydraulic modified sulfur mortar prepared in Example 2 is not burned in the torch combustion test, whereas the general modified sulfur mortar of Comparative Example 2 is a high molecular compound, so that sulfur is melted and burned to melt. This falling phenomenon occurred.

Experimental results 4. Comparative results of deterioration of mortar surface

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 hydraulic modified sulfur mortar prepared in Example 2 and the surface of the ordinary Portland cement mortar were observed after each of about 5 minutes of fire using a torch for combustion. The results are shown in FIG. 5. .

Analyzing the experimental results shown in FIG. 5, the surface of the hydraulic modified sulfur mortar prepared in Example 2 after the torch combustion test showed little cracking, whereas fine cracking occurred on the surface of the ordinary Portland cement mortar. there was. In fact, during the combustion test, small pieces bounced out in various directions with a popping sound on the surface of the specimen. Usually, about 2 to 5% by weight of water is always present inside the Portland cement mortar, and the presence and voids of this water adversely affect long-term durability, especially cement mortar, especially in torch burning tests. If you use a torch on the concrete, the moisture inside the sample evaporates and comes out of the surface of the specimen, so you can easily see that the surface of the specimen pops and the tiny pieces of water are splashed in various directions, causing a fine spider-like crack on the surface. This is commonly referred to as degradation.

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.

Claims (39)

Sulfur,
As the sulfur modifier, 1) 0.1 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 heterocyclic amines based on 100 parts by weight of the sulfur. Are mixed,
The heterocyclic amines include pyridine, quinoline, isoquinoline, acridine, acrrodine, pyrrole, piperazine, pyrrolidone and their analogs, Modified sulfur binder, characterized in that at least one selected from the group consisting of isomers of pyridine, isomers of pyridine
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 0.1 to 100 parts by weight based on 100 parts by weight of sulfur, 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. .
The method of claim 4, wherein the melt mixing is performed at a temperature in the range of 120 to 160 ° C. 6.
The method for producing a modified sulfur binder according to claim 4, wherein the alkylamines are vaporized in a range of 0.01 to 100.0 Pa 占 s of the reaction product by melt mixing.
The method of claim 4, wherein the melt mixing is terminated when the viscosity at 140 ° C. of the reaction product by melt mixing is in the range of 0.01 to 100.0 Pa · s.
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 Pa.s, 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.
The method of claim 4, wherein the liquid modified sulfur binder is cooled at a temperature of up to 120 ° C. to obtain a solid modified sulfur binder.
Sulfur, 0.1 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 aggregate 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) 0.1 to 3 parts by weight of a high performance water reducing agent,
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, 0.1 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,
Hydraulically modified sulfur material, characterized in that it comprises 80 to 400 parts by weight of the aggregate relative to 100 parts by weight of the combined 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 ° C. Method of preparation.
The dicyclopentadiene-based modifier is mixed in the range of 0.1 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. 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.
The method for producing a hydraulically modified sulfur material composition according to claim 25, wherein the melt mixing is performed at a temperature in the range of 120 to 160 ° C.
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 ° C. 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-state modified sulfur binder and the hydraulic material,
And said aggregate is mixed within the range of 80 to 400 parts by weight based on 100 parts by weight of the solid modified sulfur binder and the hydraulic material.
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 DEG C, followed by cooling and demolding to obtain a hydraulically modified sulfur material.
Sulfur, 0.1 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 of the aggregate with respect to 100 parts by weight of the modified sulfur binder.
34. The method of 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, melt mixing 0.1 to 100 parts by weight of a dicyclopentadiene-based modifier with respect to 100 parts by weight of sulfur, and 0.01 to 200 parts by weight of alkylamine based on 100 parts by weight of sulfur at 120 to 160 ° C. To produce a liquid modified sulfur binder,
(B) Combustible modified sulfur mixture, characterized in that the liquid modified sulfur binder 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 preparing the material composition.
(A) Sulfur, melt mixing 0.1 to 100 parts by weight of a dicyclopentadiene-based modifier with respect to 100 parts by weight of sulfur, and 0.01 to 200 parts by weight of alkylamine based on 100 parts by weight of sulfur at 120 to 160 ° C. To produce a liquid modified sulfur binder,
(B) cooling the liquid modified sulfur binder at a temperature of up to 120 ° C. to obtain a solid modified sulfur binder,
(C) After the solid-state modified sulfur binder is melted at a temperature of up to 100 ° C, 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. Method for producing a flammable modified sulfur material composition.
Sulfur,
0.1 to 100 parts by weight of a dicyclopentadiene-based modifier based on 100 parts by weight of the sulfur,
0.01 to 200 parts by weight of alkylamines based on 100 parts by weight of sulfur;
80 to 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,
A method for producing a combustible modified sulfur material composition, characterized in that the liquid-modified sulfur material composition is prepared by melt mixing at 120-160 ° C. for 0.01 to 3 hours.
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 ° C, cooled and demolded to obtain a flammable modified sulfur material.

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