KR20060101878A - Modified sulfur binder and method for preparing the same - Google Patents

Abstract

The present invention relates to a modified sulfur binder having excellent storage stability in the liquid phase, and includes a dicyclopentadiene-based modifier of 2 to 4% by weight of substantially 96 to 98% by weight of sulfur and an oligomer of at least trimer of cyclopentadiene. It includes a molten reaction product, characterized in that the tetragonal crystal content of sulfur in the molten reaction product ranges from 40 to 80% by weight. The reformed sulfur binder exhibits mechanical properties equivalent to those of conventional binders and solid reformed sulfur binders, which are known in the related art, and changes in physical properties such as viscosity in the liquid storage process are suppressed as much as possible. In addition, the liquid reformed sulfur binder has a merit that can be applied in various forms because it can suppress the supercooling phenomenon which has been particularly problematic during the manufacture of the conventional solid reformed sulfur binder even in the process of solidifying for long distance transportation, small amount use, and the like. .

Modified Sulfur Binder, Modifier, Dicyclopentadiene, Pretreatment, Liquid

Description

Modified Sulfur Binder and Method for Preparing the Same

FIG. 1 shows the results of measuring the hardness (Shore D) over time during the cooling of the pure sulfur melted at 140 ° C. in Example 2 and the molten samples 1, 3 and 5 of Example 1, respectively. Drawing,

2A and 2B are electron micrographs of the crystal structure observed after solidifying Samples 1 and 3 in Example 2, respectively, and

3 is a view showing the degree to which the viscosity of the liquid samples 2 to 5 prepared in Example 3 of the present invention changes with time during storage at 130 ° C.

The present invention relates to a modified sulfur binder having excellent storage stability in the liquid phase. More specifically, the present invention exhibits mechanical properties equivalent to those of the conventionally known reformed sulfur binder, and at the same time, excellent storage stability in the liquid phase, and inefficient factors such as subcooling in the process of converting them from the liquid phase to the solid phase can be suppressed as much as possible. The present invention relates to a modified sulfur binder and a method for producing the same.

Sulfur melts at temperatures above 119 ° C and is a solid at room temperature. By using the characteristics of sulfur components, technologies that apply to civil engineering and construction fields such as packaging materials and building materials have been continuously developed. Such sulfur components are known to be used as binders for the production of civil and building materials in the form of moldings by mixing with various aggregates. However, in the case of a molded article using pure sulfur as a binder, many problems are caused in physical properties such as brittleness, and its application is limited.

In order to solve the problems caused when using pure sulfur as a binder, a method of using a specific compound for addition as a modifier has been studied. In particular, as such a compound for addition, dicyclopentadiene is known to have a low price and excellent economical efficiency, and to have a good effect on the development of mechanical strength (New Uses of Sulfur-II, pp. 68 to 77 ( 1978).

In this regard, US Pat. No. 4,025,352 discloses a process for producing sulfur-modified concrete in which a binder of molten sulfur and dicyclopentadiene is mixed with an aggregate and the mixture is cooled. The patent discloses that sulfur, dicyclopentadiene and aggregate can be achieved under the conditions of temperature-mixing time of a particular region to achieve the advantages of excellent solvent, salt, acid and alkali resistance. . However, the patent proposes a condition for the manufacturing process of the concrete composition, which basically assumes the presence of aggregate, and thus the storage stability in the liquid phase of the binder composed of sulfur and modified components prior to mixing with the aggregate. The present invention is primarily conceptually different from the present invention to be secured.

Meanwhile, in the art, a method of preparing a modified sulfur binder by reacting sulfur and dicyclopentadiene in a solid form, and then mixing the aggregate with aggregate to produce concrete, etc. has become a technology trend. In addition, as disclosed in Japanese Patent Application Laid-Open Nos. 2-25929 and 2-28529, vinyl toluene, dipentene, and other olefin oligomers are added to improve the properties of sulfur, Examples of use as adhesives, waterproofing agents, and the like are also known.

Typically, the reaction of dicyclopentadiene and sulfur can be viewed as a kind of polymerization reaction. That is, sulfur and dicyclopentadiene initially react, and then a polymer is produced by a chain reaction with sulfur radicals. However, in the subsequent reaction between dicyclopentadiene and sulfur, a large amount of heat is generated, and the reaction control is difficult because the temperature and the viscosity increase sharply, and the solidification is rapidly solidified at room temperature, thereby making the molding impossible. To avoid this, US Pat. 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). . In addition, Japanese Patent Application Laid-Open No. 2-28529 and its corresponding U.S. Patent No. 4,391,969 are polymers reacted with a modifier containing sulfur and 2 to 20% by weight of a cyclopentadiene oligomer mixture-dicyclopentadiene. A modified sulfur binder is disclosed, wherein the content of the cyclopentadiene oligomer in the modifier is required to be at least 37%. According to the patent, a process of heating the composition of sulfur and a modifier is followed by curing, wherein such cyclopentadiene oligomers, such as trimers, tetramers and pentamers of cyclopentadiene, It means oligomers other than dicyclopentadiene. In particular, there is a feature in that not only dicyclopentadiene but also a trimer or more oligomer of cyclopentadiene is added in a predetermined amount or more as a modifier.

However, the above-mentioned prior art does not relate to the manufacturing conditions (temperature, concentration of dicyclopentadiene, etc.) in the case of addition of dicyclopentadiene and the properties of the binder, and further to reheat the solid phase binder to be mixed with the aggregate. Considering the fact that the mixing conditions for solving the curing phenomenon due to the additional polymerization caused in the process are not identified, prior art is known that specifies the conditions of the improved solid-state reforming sulfur binder manufacturing process conditions.

WO 03/076360 A1, for example, melt-mixed at least 0.1 part by weight of cyclopentadiene and less than 2 parts by weight to 135 to 155 ° C in a closed state with respect to 100 parts by weight of sulfur and the viscosity at 140 ° C. Discloses a method for producing a reformed sulfur binder, which comprises the step of bringing? To 0.05 to 1.2 Pa · s and then cooling to 135 ° C. or less. In addition, in the Example, after adding heated dicyclopentadiene to molten sulfur and making it react at 140 degreeC, heating is stopped and cooled at room temperature at the time which becomes 0.1 Pa.s. However, in the prior art, since cyclopentadiene is used in an amount of less than 2 parts by weight based on 100 parts by weight of sulfur, it is difficult to obtain a sulfur modification effect required in the present invention.

On the other hand, most of the above-described prior art is prepared separately in the solid phase of the reaction product of the modified components such as sulfur and dicyclopentadiene, and then applied to the construction or civil engineering materials such as concrete, asphalt, etc. later using aggregate. The method of mixing with aggregate at a specific ratio under heating or by melting and mixing sulfur, modified components and aggregate in one step under specific process conditions is cooled. However, the process of cooling the hot molten binder to a solid phase has been pointed out as a problem in terms of productivity and energy efficiency, and facility investment for solidification is also acting as a factor in manufacturing cost.

In addition, in the cooling step for actual solidification, the reaction product tends to exist in a supercooled state, that is, in a slime state, rather than in a solid state, even though it is a room temperature condition. Therefore, since the supercooled state requires a considerable time until the solidification is eliminated, there is a serious disadvantage in terms of time and economics. In particular, as the content of the modifying component increases, the polymerization reaction increases, such a supercooling phenomenon becomes worse.

In this regard, the inventors of the present invention not only know the composition, process conditions, etc. for the manufacture of a binder suitable for the liquid form to date, but also find that a technical problem that is not considered in manufacturing a conventional solid form binder should be solved. It was. In particular, it should be able to be stored above a certain temperature prior to mixing with the aggregate, and the way to suppress the change of physical properties as much as possible during this storage period should be considered. In addition, it is often required to store and transport the liquid reformed sulfur binder in a solid phase even in view of the above-mentioned problems in the solid reformed sulfur binder. It is also an important consideration to ensure that the same phenomenon can be suppressed as much as possible.

On the contrary, the present inventors have continuously studied to prepare a method for producing a reformed sulfur binder in a liquid phase, and as a result, the composition and process conditions of a conventionally known reformed sulfur binder material may satisfy the requirements of the liquid phase. It has been found that it is not possible to develop the properties and manufacturing process of the modified sulfur binder to achieve this. In addition, it has been found that the supercooling phenomenon can be effectively suppressed even when it is specifically required to solidify the liquid reformed sulfur binder.

Accordingly, it is an object of the present invention to provide a reformed sulfur binder in which a change in physical properties such as viscosity can be suppressed as much as possible while exhibiting mechanical properties equivalent to or higher than those of a conventional solid reformed sulfur binder in a liquid phase.

Another object of the present invention is to provide a reformed sulfur binder that can be stored and transported as well as securing the liquid stability of the reformed sulfur binder in the liquid phase, and in particular, in the case where solidification is required, to suppress the supercooling phenomenon during the cooling process as much as possible. .

Another object of the present invention is to provide a method for producing such a modified sulfur binder.

In order to achieve the above object, the first aspect provided in accordance with the present invention relates to a liquid reformed sulfur binder, dicyclo which is substantially free of oligomers of 96 to 98% by weight of sulfur and cyclopentadiene. It comprises a molten reaction product of 2 to 4% by weight of pentadiene-based modifier, characterized in that the tetragonal crystal content of sulfur in the reaction product ranges from 40 to 80% by weight.

A second aspect provided according to the present invention relates to a method for producing a liquid reformed sulfur binder, wherein a dicyclopentadiene-based modifier 2 substantially free of oligomers of 96 to 98% by weight of sulfur and a terpolymer of cyclopentadiene 2 And reacting ˜4 wt.% So that the orthorhombic crystal content of sulfur is in the range of 40 to 80 wt.% In the reaction product under melting conditions of 135 to 145 ° C.

A third aspect provided in accordance with the present invention relates to a process for producing the above-mentioned liquid modified sulfur binder, optionally in solid form, comprising: a) substantially oligomers of 96 to 98% by weight of sulfur and at least trimers of cyclopentadiene. Reacting 2 to 4% by weight of a dicyclopentadiene-based modifier which is not contained in the reaction product so as to have an orthorhombic crystal content of sulfur in the reaction product in a range of 40 to 80% by weight under a melting condition of 135 to 145 ° C; And

b) cooling the reaction product in the molten state until the Vickers microhardness number reaches 15-30.

Hereinafter, the present invention can be achieved by the following description with reference to the accompanying drawings.

As described above, the present invention relates to a liquid reformed sulfur binder useful as a binder in the construction or civil engineering fields, such as concrete, asphalt, and particularly, has excellent storage stability in the liquid phase. In the present invention, the "storage stability in the liquid phase" is described based on the viscosity, which is one of the most important physical properties of the produced reformed sulfur binder in the liquid phase, specifically, the maximum viscosity characteristics in the storage temperature range of the produced reformed sulfur binder. This means that it can be kept stable.

In addition, in the present invention, the expression “substantially free of oligomers of at least trimers of cyclopentadiene” indicates that at most 0.5 wt%, preferably at most 0.2, of oligomers of at least trimers of cyclopentadiene as impurities in the modifier. It can be contained by weight percent.

The reformed sulfur binder provided in accordance with the present invention is a reaction of sulfur with a small amount of modifier under melting conditions, and as a result of the reaction, polysulfide is produced to give a physical property improving effect according to the reforming. In this regard, more specific reaction mechanisms are described in US Pat. No. 4,311,826, which is incorporated by reference in the present invention.

Sulfur that can be used in the present invention may use conventional sulfur elements, and in particular, sulfur derived from the refining process of crude oil or natural sulfur derived from mines.

Modifiers used for sulfur modification in the present invention are dicyclopentadiene-based modifiers. Such modifiers include dicyclopentadiene (DCP) as a modifier and include cyclopentadiene (CP) and / or derivatives thereof (e.g., methylcyclopentadiene (MCP), methyldicyte) in the dicyclopentadiene. Clopentadiene (MDCP)) may optionally be further contained (e.g., a modifying component other than DCP may be up to about 20% by weight of the total modifying component). In addition, the modifier may be provided in the form of a mixture of dipentene, styrene monomer, vinyl toluene and the like. Of particular note is that the modifier does not intentionally contain at least a certain amount of oligomers of at least trimers of cyclopentadiene, rather than as disclosed in the foregoing prior arts, for example US Pat. Nos. 4,311,826 and 4,391,969, rather The use of modifiers in a form that is substantially free of such oligomers can also achieve the intended technical features. Therefore, it is to be understood that the present invention enables the use of dicyclopentadiene alone as a modifying component. In particular, the modifier may be provided in a form in which the modifying component typically has a purity of preferably at least about 80% by weight, more preferably at least 90% by weight, and most preferably at least 98% by weight. For exemplary compositions of this type of modifier, about 65-75 wt% dicyclopentadiene, about 10-20 wt% cyclopentadiene, about 10-20 wt% derivatives thereof (MCP, MDCP, etc.), and others About 0.1-1.5 weight percent of the component.

In the prior art, the use of unrefined fractions, such as cracker residues in refinery naphtha cracking processes, leads to the generation of adverse odors during manufacturing or use, and due to various substances that are difficult to analyze, It was difficult to fully prove the relationship between. However, in the case of the present invention, it is differentiated by using relatively purified dicyclopentadiene.

On the other hand, according to the present invention, a rapid temperature rise of the reactants occurs due to the exothermic reaction by polymerization of sulfur and the modifier in the production of the modified sulfur binder. This may cause the formation of by-products and run-away reactions, it is preferable to slowly add a certain amount of modifier to prevent this. For example, once the sulfur is melted to about 140 ° C., the modifier is slowly added and reacted under melting conditions of about 135 to 145 ° C. (preferably with stirring). At this time, the reaction time is controlled according to the amount of the modifier used, the reaction product is reacted to the point where the tetrahedral crystal content of sulfur in the reaction product is in the range of about 40 to 80% by weight, preferably about 60 to 80% by weight. In particular, the reason why the tetragonal crystal content of sulfur in the present invention is limited to the aforementioned range is because the chemical modification degree of sulfur can be expressed in the desired physical properties and performance as a binder within the above range. For example, when sulfur and dicyclopentadiene-based modifiers are used at 97: 3, the content range of the tetragonal crystals will be reached after typically about 1 to 3 hours at about 140 ° C.

In this regard, the content of the tetragonal crystal may be understood as a concept based on the solid phase, but in the process of measuring the tetragonal crystal content in the modified sulfur binder using solid phase scanning calorimeter (DSC), etc. Since it involves melting, it can be applied to liquid reformed sulfur binders without any particular difficulty.

The reaction product preferably exhibits a viscosity (based on 135 ° C.) of about 10 to 800 cP, more preferably about 10 to 100 cP, upon completion of the reaction.

According to the present invention, the amount of the modifier is used at a level of about 2 to 4% by weight, more preferably about 2 to 3% by weight, and most preferably about 3% by weight, based on the total weight of the reactants. If a modifier of less than 2% by weight is used, the content of polysulfides falls short of the above range because the content of tetragonal crystals in the reaction product, which gives a measure of reaction progress, is not particularly differentiated from sulfur before the reaction. It is difficult to expect the effect of sulfur reforming. On the other hand, if the amount of the modifier exceeds 4% by weight, the viscosity increases significantly due to the continuous polymerization in the liquid storage process (for example, when stored at 130 to 140 ° C, which is a typical storage temperature).

In this regard, it is interesting to note that even when the amount of the modifier exceeds 4% by weight, even though the tetragonal content of sulfur in the reaction product can meet the required level, the range defined in the present invention (2 to 4% by weight) results in a significant viscosity increase over time in the liquid storage process. This means that even when dicyclopentadiene is used alone as the modifier, the liquid storage stability of the reformed sulfur binder is ensured by adjusting the amount thereof to a specific range, and the reaction product is based on the preparation of the solid reformed sulfur binder. It differs from the prior art which requires the use of a considerable amount of oligomers of at least trimers of cyclopentadiene to maintain a constant viscosity of.

In particular, as described below, when the modified sulfur binder prepared in the liquid phase exceeds 4% by weight in order to achieve the required level of hardness to act as a factor causing the super-cooling phenomenon of the product For this reason, the solidification is not performed in a short time even at a temperature significantly lower than the melting point of sulfur, for example, at room temperature, and causes a problem of leaving a lot of time in fact.

According to the present invention, one or two or more of various additives may be used in consideration of characteristics required in the field of application of the modified sulfur binder which is the final product.

In this connection, about 0.1 to 5% by weight of a plasticizer such as carbon or carbon black may be additionally used as a super-addition to increase the dispersion in the reaction process, based on the total weight of sulfur and modifier. have. In addition, in response to the trend of requiring aesthetic or identification capabilities in construction or civil engineering materials, various pigments known in the art, in particular inorganic pigments (eg iron oxide, etc.), are also based on the total weight of sulfur and modifiers. By adding 0.1 to 5% by weight, modified sulfur binders of various colors can be prepared. In addition, isoamyl acetate or phenethyl alcohol, preferably phenethyl alcohol, in the reaction process for the purpose of fragrance in order to reduce the discomfort due to the irritating smell of sulfur itself, based on the total weight of sulfur and modifier, 2 weight percent may be added. As such, the modified sulfur binder to which the aromatic component is added may improve workability by providing vanilla, rose, and the like during manufacture or construction.

As described above, the storage / transport temperature in the liquid phase of the reaction product obtained by the reaction of sulfur with the modifier is preferably about 130 to 140 ° C, more preferably about 135 ° C. For example, the viscosity range of the liquid reformed sulfur binder during two weeks of liquid storage at about 130 ° C. is preferably about 10-1000 cP, more preferably about 10-500 cP.

In addition, in the present invention, it is preferable to set the storage / transfer temperature of the liquid reformed sulfur binder to be about 2 to 5 ° C. lower than the reaction temperature of the sulfur and the modifier described above. For example, if the reaction temperature is about 140 ° C, the storage temperature is on the order of about 135 ° C.

On the other hand, the liquid reformed sulfur binder according to the present invention can be transformed into a solidified form, for the purpose of long-distance transport or small amounts of use. That is, the molten reaction product of sulfur and modifier is cooled until the beaker microhardness reaches about 15-30, preferably about 20-30. In this regard, it should be understood that the present invention includes not only the molten reaction product but also the case where the reformed sulfur binder is once solidified.

According to a preferred aspect of the present invention, once the liquid reformed sulfur binder is reacted after or during storage in a reactor, storage tank or separate facility, it is cooled to about 120 to 125 ° C, more preferably around 125 ° C. It is separated from the distributor or depositer on a conveying means, such as a conveyor steel belt, and cooled as the conveyor belt progresses. At this time, the cooling atmosphere on a conveyor belt is not specifically limited, For example, normal temperature is possible. This aspect has the advantage of further suppressing the deterioration of the supercooling phenomenon. In particular, the solid-state modified sulfur binder prepared according to the above aspect is advantageous in terms of handling since it has a tendency to self-granulate in the form of flakes during cooling. In addition, it can also be cooled in the form of hemispheres, pellets and the like.

The reformed sulfur binder of the present invention can be applied to various applications such as structural materials, coating materials, waste treatment materials, etc. in civil engineering / building special materials, underground, sea, or underwater. In particular, it can be applied as a substitute for conventional portland cement, asphalt and the like. Typically, the modified sulfur binder of the present invention may be used in combination with various aggregates, and is not particularly limited as such aggregates, and conventional finely divided aggregates and coarse aggregates may be used. In addition to these aggregates, industrial waste incinerators, fly ash, blast furnace slag, coal ash, silica fume, blast furnace cement, waste sand, and the like may be used as additional aggregates or fillers. The mixing ratio of the modified sulfur binder and aggregate is determined in consideration of mechanical properties such as aggregate type, compressive strength and flexural strength, as well as slump value during mortar pouring and flow of the mixture. The mixing ratio of the modified sulfur binder and aggregate (for example, fine aggregate such as sand) may be adjusted in a range of about 1: 1.5 to 1: 2 based on weight.

In addition, when mixing with the modified sulfur binder and the aggregate of the present invention, the aggregate may be preheated prior to mixing with the binder. In addition, the reformed sulfur binder may also be preheated prior to mixing by applying appropriate heat depending on the properties of the reformed sulfur binder (particularly in the case of solid phase). The preferred mixing temperature of the modified binder and aggregate is about 130 to 140 ° C. Indirect heating rather than direct heating is used to prevent local rapid rise in temperature during the temperature rise or maintenance of the mixing temperature. It is preferable to adopt.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples.

Example 1

Sulfur and dicyclopentadiene (DCP) were reacted using reactants of the composition shown in Table 1 (based on 100 g total). At this time, the reaction was maintained at the temperature while slowly adding dicyclopentadiene to the sulfur preheated at 140 ℃. In addition, considering that the reaction of sulfur and dicyclopentadiene is exothermic, the temperature increase was not caused, and the total reaction time was about 3 hours. Physical properties (density and viscosity) in the reaction product, and the tetragonal crystal content of sulfur are shown in Table 1 below.

Sample Composition (% by weight) Properties Content of tetragonal crystal ³ (% by weight) brimstone DCP Density ¹ (g / cm 3) Viscosity ² (cP) One 99 One 1.92 11 90 2 98 2 1.90 13 78 3 97 3 1.87 25 67 4 96 4 1.86 43 60 5 95 5 1.83 65 52

¹ : measured according to ASTM D70 at 25 ° C.,

² : measured according to ASTM D4402 at 135 ° C, and

³ : Mean content of tetragonal crystals of sulfur in the modified sulfur binder measured under the trade name Pyris 6 of PerkinElmer.

Example 2

In order to examine the effect of the amount of the modifier on the mechanical properties of the modified sulfur binder, pure sulfur melted at 140 ° C., and samples 1, 3, and 5 in the molten state of Example 1 were cooled, and the hardness over time. D) was measured according to ASTM 2240. The results are shown in FIG.

From FIG. 1, it can be seen that Sample 1 gradually decreases in hardness as time passes, such as pure sulfur, while Samples 3 and 5 gradually increase in hardness.

In addition, after solidifying sample 1 and sample 3 at room temperature, the crystal structure was observed through the electron microscope. The results are shown in FIGS. 2A and 2B, respectively.

According to FIG. 2, sample 1 has a very irregular and large number of crystals, while sample 3 has a relatively small crystal and has a regular arrangement. This shows that in case of sample 1, crystal structure is similar to that of pure sulfur due to excessive crystal growth due to insufficient reforming, while in case of sample 3, excessive chemical growth is alleviated by sufficient chemical modification by using an appropriate amount of modifier. Point. Therefore, it can be seen that Sample 3 can impart excellent characteristics in brittleness, etc. at the time of forming later than Sample 1.

Example 3

The modified sulfur binder (Samples 2 to 5) produced by the reaction according to Example 1 was stored at a temperature of 130 ° C., and the viscosity change over time was observed. The results are shown in FIG.

As shown in FIG. 3, even when dicyclopentadiene alone is used as the modifier, when the amount of modifier used is adjusted to 2 to 4 wt% (samples 2 to 4), even when 6 weeks or more are stored in the liquid phase, stabilized viscosity characteristics Indicated. On the other hand, when 5% by weight of dicyclopentadiene was used as a modifier (Sample 5), after 3 weeks in liquid storage, although the tetragonal crystal content of sulfur in the binder satisfied the required level of 52% by weight, 10000 cP or more. In summary, it has been found that the amount of the modifier used is an important factor in the liquid shelf life of the reformed sulfur binder. In addition, in view of the more stable storage properties of Samples 2 and 3, it can be seen that the preferred amount of modifier is 2 to 3% by weight.

Example 4

In order to evaluate the mechanical properties of the modified sulfur binder according to the present invention, the modified sulfur binder of Sample 3 (135 ° C.) and sand of 0.4 to 0.8 mm (135 ° C.) were weighted based on 1 in a self-made carbon steel mixer. Mortar (SPC) was prepared by mixing at: 1.5, and slump and strength tests were performed. At this time, the slump cone, the plate, and the compaction rod were preheated to about 135 ± 5 ° C. in order to prevent a sudden drop in temperature during the slump test. The results are shown in Table 2 below, and compared with the case of using a conventional general Portland cement mortar for comparison purposes.

Strength test results according to slump and age of mortar Slump ¹ (cm) Compressive strength ² (MPa) Flexural Strength ³ (MPa) 3 hours 1 day 1 week 3 hours 1 day 1 week OPC ⁴ 14.0 - - 35.1 - - 5.1 SPC 12.3 40.6 47.5 42.2 7.0 8.1 9.7

¹ : measured according to the test method specified in the KS F 2402 concrete slump test method,

² : measured according to the compressive strength test method of KS L 5105 hydraulic cement mortar,

³ : measured according to the flexural strength test method of KS F 2408 concrete, and

⁴ : general Portland cement mortar (cement: sand weight mixing ratio 1: 3).

Example 5

In the present invention, after evaluating the degree of supercooling in the solidification process, each of 5g samples were obtained from the molten reaction product (samples 2 to 5) at 140 ° C. and then cooled at room temperature. The time required for the beaker microhardness to reach 15 (minimum) to 30 (maximum) was measured. At this time, the beaker microhardness number was measured by Matsuzawa brand name DMH-1. The test results are shown in Table 3 below.

Sample Total time spent solidifying (minutes) 2 10 to 15 3 15-20 4 20-30 5 50 to 60

In view of the above table, it can be seen that samples 2 to 4 corresponding to the reformed sulfur binder in the liquid phase according to the present invention can suppress the severe supercooling phenomenon compared to sample 5, so that the time required for solidification is considerably low.

As described above, the reformed sulfur binder according to the present invention exhibits the same or more mechanical properties as those of conventional portland cement and solid-state reformed sulfur binder, and has the effect that the change of physical properties such as viscosity in the liquid storage process can be suppressed as much as possible. Have In addition, according to the present invention, when the liquid reformed sulfur binder is solidified for long distance transportation, small amount use, etc., it also has an advantage of suppressing the supercooling phenomenon as much as possible. Therefore, the modified sulfur binder is expected to be widely applied in the manufacturing process of various construction or civil engineering building materials such as concrete, asphalt.

Simple modifications and variations of the present invention can be readily used by those skilled in the art, and all such variations or modifications can be considered to be included within the scope of the present invention.

Claims (13)

A molten reaction product of 96 to 98% by weight sulfur and 2 to 4% by weight of a dicyclopentadiene-based modifier that is substantially free of oligomers of at least trimers of cyclopentadiene, wherein Liquid reformed sulfur binder, characterized in that the crystal content in the range of 40 to 80% by weight. The modified sulfur binder of claim 1, wherein the dicyclopentadiene-based modifier comprises dicyclopentadiene alone as a modifying component. The method of claim 1, wherein the dicyclopentadiene-based modifier further comprises dicyclopentadiene (DCP), cyclopentadiene (CP), derivatives of dicyclopentadiene, derivatives of cyclopentadiene or mixtures thereof as a modifier. Liquid reformed sulfur binder, characterized in that it contains. The reformed sulfur binder of claim 1, wherein the molten reaction product has a viscosity of 10 to 800 cP (based on 135 ° C.). The liquid reformed sulfur binder according to claim 1, wherein the oil reforming binder has a viscosity of 10 to 1000 cP at a storage temperature of 130 ° C. Sulfur tetragonal crystals of sulfur in the reaction product of 96 to 98% by weight sulfur and 2 to 4% by weight of a dicyclopentadiene-based modifier substantially free of oligomers of at least trimers of cyclopentadiene under melting conditions of 135 to 145 ° C. Method for producing a liquid reformed sulfur binder comprising the step of reacting the content in the range 40 to 80% by weight. The production method according to claim 6, wherein at least one component selected from the group consisting of plasticizers, pigments and fragrances is further added in the reaction step. The method according to claim 7, wherein the plasticizer is carbon or carbon black, and the amount of the plasticizer is 0.1 to 5% by weight based on the total weight of the sulfur and the modifier. 8. The process according to claim 7, wherein the amount of the pigment added is 0.1 to 5% by weight based on the total weight of sulfur and modifier. The method according to claim 7, wherein the fragrance is isoamyl acetate or phenethyl alcohol, and the addition amount thereof is 0.01 to 2% by weight based on the total weight of sulfur and the modifier. 8. The production method according to claim 7, wherein the storage / transport temperature range of the produced liquid reformed sulfur binder is 130 to 140 ° C. The production process according to claim 11, wherein the storage / transport temperature of the reformed sulfur binder is set to be 2 to 5 ° C lower than the reaction temperature of the sulfur and the modifier. a) from 96 to 98% by weight of sulfur and from 2 to 4% by weight of a dicyclopentadiene-based modifier, which is substantially free of oligomers of at least trimers of cyclopentadiene, under the melting conditions of 135 to 145 ° C. Reacting so that the crystallite content is in the range of 40 to 80% by weight; And b) cooling the reaction product in the molten state until the beaker microhardness reaches 15 to 30; Solid phase modified sulfur binder manufacturing method comprising a.

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