KR101319942B1 - Sulfur Polymer Cement and The Fabrication Method Thereof - Google Patents

Abstract

Sulfur polymer cements and methods of making the same are disclosed. According to a preferred embodiment of the present invention, as a sulfur and sulfur modifier, 0.1 to 100 parts by weight of dicyclopentadiene modifier and 100 parts by weight of amide modifier based on 100 parts by weight of sulfur. Sulfur polymer cement is provided, characterized in that 1 to 100 parts by weight are melt mixed.
According to the present invention, it is possible to re-melt at a temperature of 100 ℃ or less, the viscosity is low, the effect of excellent fluidity and workability, and also because the low viscosity of the sulfur polymer cement is dissolved in water, dissolved sulfur polymer cement particles They can be evenly distributed there is an advantage that the quality can be expressed uniformly.

Description

Sulfur Polymer Cement and The Fabrication Method Thereof}

The present invention relates to a sulfur polymer cement and a method for producing the same, and more particularly, to a sulfur polymer cement having a physical property capable of remelting at a temperature of 100 ° C. or less and a method for producing the same.

Generally, cement is a bonding curing agent widely used for construction structures and other facilities such as civil engineering and construction, and often refers to Portland cement containing lime, silica, alumina, iron oxide and the like.

However, cement is widely used as a bonding material for bonding materials and materials, and the kinds of such cements that can be widely used in construction structures and facilities are various other than Portland cement.

On the other hand, various technologies for the construction of construction structures and facilities, etc., have been researched and developed by using sulfur as such cement which can be used for construction structures and facilities, in place of or replacing conventional Portland cement.

Especially, it can be used as packaging material, construction material, civil engineering material or waste solidification material. In this regard, various technologies have been researched and developed in Korea, USA and Japan, and many patents have been filed and registered to be.

Cement manufactured by using sulfur is called as various names such as sulfur polymer cement, modified sulfur, plasticized sulfur, or modified sulfur binder because it functions as cement through the physical and chemical treatment of sulfur cement or sulfur. The term polymer cement (SPC: Sulfur Polymer Cement) will be used interchangeably.

As described above, these sulfur polymer cements can have various physical and chemical properties depending on the physical and chemical treatments of sulfur. Particularly, the sulfur polymer cements have various physical and chemical properties depending on the chemical composition of sulfur polymer cement, Research is underway.

In order to overcome the disadvantages such as weak chemical resistance, strength and durability of general portland cement concrete, sulfur polymer cement is used as a binder instead of Portland cement and mixed with various aggregates to produce mortar or concrete A sulfur polymer cement concrete technique was developed.

Particularly, Korean Patent No. 10-0911659 discloses that a sulfur polymer cement having physical properties capable of remelting at a temperature of 100 ° C. or less can be produced using dicyclopentadiene-based and heterocyclic amines as modifiers.

However, in the case of Korean prior art such as Korean Patent No. 10-0911659, it is necessary to use a large amount of dicyclopentadiene modifier in order to enable re-melting at a temperature of 100 ° C or less. Therefore, quality control of the manufactured sulfur polymer cement It is difficult to ensure the homogeneity of the product. Therefore, when the product is used at the actual work site, problems such as securing the quality of the concrete product and securing the product stability are raised.

In addition, since the sulfur polymer cement is hydrophobic, the sulfur polymer cement particles are mutually bonded to each other even when the sulfur polymer cement does not dissolve or dissolve in the actual water, resulting in a problem that the dissolved sulfur polymer cement particles are not uniformly dispersed among the Portland cement or aggregates.

Accordingly, the conventional concrete using the sulfur polymer cement has a problem that the quality of the concrete product can not be uniformly developed.

In order to solve the conventional problems as described above, the present invention is to propose an excellent sulfur polymer cement and a method of manufacturing the same that can be re-melted at a temperature of less than 100 ℃ while ensuring a uniform quality and product stability. .

In addition, sulfur polymer cement and its manufacturing method which improve the hydrophobicity and increase the hydrophilicity of sulfur polymer cement, solubility in water, and dissolved sulfur polymer cement particles can be evenly dispersed in concrete so that the quality can be expressed uniformly. Is to suggest.

Still other objects of the present invention will be readily understood through the following description of the embodiments.

In order to achieve the object as described above, according to an aspect of the present invention there is provided a sulfur polymer cement.

According to a preferred embodiment of the present invention, sulfur; And 0.1 to 100 parts by weight of a dicyclopentadiene-based modifier based on 100 parts by weight of the sulfur as a sulfur modifier. And 1 to 100 parts by weight of amides (amide) based on 100 parts by weight of the sulfur is melt mixed.

The amides may be at least one of acid amides, metal amides, and amide compounds.

And the acid amide is formamide (HCONH ₂ ), acetamide (CH ₃ CONH ₂ ), dimethylformamide (HCON (CH ₃ ) ₂ ), dimethylacetamide (CH ₃ CON (CH ₃ ) ₂ ) and benzamide ( C ₆ H ₅ CONH ₂ ) It may be at least one.

In addition, the metal amide may be at least one of sodium amide (NaNH ₂ ) and calcium amide (Ca (NH ₂ ) ₂ ).

The dicyclopentadiene-based modifier is a dicyclopentadiene (DCPD) monomer alone, or a mixture in which at least one of a cyclopentadiene (CPD) monomer, a DCPD derivative, and a CPD derivative is added to the DCPD monomer, or Cyclocyclic as a solvent in the dicyclopentadiene (DCPD) monomer alone or in a mixture in which at least one of a cyclopentadiene (CPD) monomer, a DCPD derivative, and a CPD derivative is added to the DCPD monomer. Dipentene, limonene, vinyltoluene, styrene, methylstyrene, dicyclopentene, pinen and indene are cyclic hydrocarbon compounds It may be an olefin mixture to which at least one of an indene or an aromatic hydrocarbon compound is added.

The sulfur polymer cement may be liquid or solid.

According to another aspect of the invention there is provided a method for producing sulfur polymer cement.

According to a preferred embodiment of the present invention, sulfur polymer cement, characterized in that the sulfur polymer cement by melting and mixing a dicyclopentadiene-based modifier and amide (amide) as a sulfur and the sulfur modifier. A manufacturing method is provided.

The dicyclopentadiene-based modifier may be mixed in the range of 0.1 to 100 parts by weight based on 100 parts by weight of the sulfur, and the amide may be mixed in an amount of 1 to 100 parts by weight based on 100 parts by weight of the sulfur. have.

The amides may be at least one of acid amides, metal amides, and amide compounds.

In addition, the acid amide is formamide (HCONH ₂ ), acetamide (CH ₃ CONH ₂ ), dimethylformamide (HCON (CH ₃ ) ₂ ), dimethylacetamide (CH ₃ CON (CH ₃ ) ₂ ) and benzamide (C ₆ H ₅ CONH ₂ ) It may be at least one.

In addition, the metal amide may be at least one of sodium amide (NaNH ₂ ) and calcium amide (Ca (NH ₂ ) ₂ ).

The dicyclopentadiene-based modifier is a dicyclopentadiene (DCPD) monomer alone, or a mixture in which at least one of a cyclopentadiene (CPD) monomer, a DCPD derivative, and a CPD derivative is added to the DCPD monomer, or Cyclocyclic as a solvent in the dicyclopentadiene (DCPD) monomer alone or in a mixture in which at least one of a cyclopentadiene (CPD) monomer, a DCPD derivative, and a CPD derivative is added to the DCPD monomer. Dipentene, limonene, vinyltoluene, styrene, methylstyrene, dicyclopentene, pinen and indene are cyclic hydrocarbon compounds It may be an olefin mixture to which at least one of an indene or an aromatic hydrocarbon compound is added.

The melt mixing may be made in a temperature range of 120 ~ 160 ℃.

As described above, according to the sulfur polymer cement according to the present invention and its manufacturing method, there is an effect excellent in workability that can ensure uniform quality and product stability at a temperature of 100 ° C or less.

It also improves hydrophobicity and hydrophilicity of sulfur polymer cement to improve fluidity and workability such as emulsification, surface activity and dispersion with water. There is an advantage that the quality of the sulfur polymer cement, such as viscosity control, reaction suppression can be expressed uniformly.

1 is a view showing a manufacturing process of sulfur polymer cement according to an embodiment of the present invention.
FIG. 2 is a view illustrating photographing and comparing changes of remelting according to temperature change of a conventional sulfur polymer cement and a sulfur polymer cement according to an exemplary embodiment of the present invention. FIG.
Figure 3 is a view showing a comparison of the state of the liquid phase changes according to the temperature change of the sulfur polymer cement according to a preferred embodiment of the present invention and sulfur polymer cement.
4 is a view showing a comparison of the state of the liquid phase change according to the reaction of the conventional sulfur polymer cement and the sulfur polymer cement according to a preferred embodiment of the present invention at 60 ℃ water in the re-melting state.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Like reference numerals are used for like elements in describing each drawing. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The terms first, second, etc. may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another.

For example, without departing from the scope of the present invention, the first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component.

And / or < / RTI > includes any combination of a plurality of related listed items or any of a plurality of related listed items.

When a component is said to be “connected” or “connected” to another component, it may be directly connected to or connected to that other component, but it may be understood that another component may exist in the middle. Should be.

On the other hand, when a component is said to be “connected” or “connected” to another component, it should be understood that no other component exists in the middle.

The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the present invention.

Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms “comprise” or “have” are intended to indicate that there is a feature, number, step, action, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings, wherein like or corresponding elements are denoted by the same reference numerals, and a duplicate description thereof will be omitted.

First, sulfur used in the present invention is a conventional sulfur monomer, and such sulfur includes natural sulfur or by-product sulfur produced by desulfurization of petroleum or natural gas, and sulfur is 120 ° C. or higher, preferably 125 to Molten sulfur heated and melted at 140 ° C. or molten sulfur transported in the liquid phase in a desulfurization plant of petroleum or natural gas may be used.

Modifiers used for sulfur modification in the present invention are amides (diamide) and dicyclopentadiene (DCPD) modifiers.

Dicyclopentadiene-based modifiers include dicyclopentadiene (DCPD) monomers as the modifying component, as disclosed in published patents in the US, Japan and Korea.

Such DCPD may be a monomer alone, or a cyclopentadiene (CPD) monomer, a DCPD derivative, a CPD derivative (eg, methylcyclopentadiene (MCP), methyldicyclopentadiene (MDCP), etc.) in the DCPD monomer. A mixture to which at least one of) is added may be used.

As an exemplary composition of such a dicyclopentadiene-based modifier, about 65 to 75 parts by weight of DCPD, about 10 to 20 parts by weight of CPD, about 10 to 20 parts by weight of derivatives thereof (MCP, MDCP, etc.), based on 100 parts by weight of the modifier, And about 0.1 to 1.5 parts by weight of the other components.

In addition, cyclic hydrocarbon compounds such as dipentene, limonene, vinyltoluene, styrene, methylstyrene, dicyclopentene, pinene ( It may be used in a mixed form with an olefin compound such as one of pinen, indene or aromatic hydrocarbon compounds.

The dicyclopentadiene-based modifier, as disclosed in Japanese Patent Laid-Open No. 2002-60491 and Korean Laid-Open Patent Publication No. 10-2005-26021, preferably has a content of DCPD monomer of about 70 parts by weight or more, and more preferably 85 parts by weight. Most of the commercial items commonly referred to as so-called dicyclopentadiene (DCPD) can be used.

On the other hand, the present invention newly applied amides (amide) as a modifier. Amides are compounds in which ammonia or amine hydrogen atoms are substituted with acyl residues. Amides called acid amides and ammonia hydrogen atoms are substituted with metals. Compounds include amides, also called metal amides, and also include all kinds of amide compound systems.

In addition, all of such amide homologs, isomers of amides and isomers of amides may be included.

Especially in the case of acid amides, RCONH ₂ having an amino group (-NH ₂ ) RCONHR 'is a secondary amide, RCONR'R ”is a tertiary amide, and R' is an alkyl group in RCONHR ', which is called an alkylamide and R' is an allyl group, and may contain all these kinds of amides. have.

Such acid amides are, for example, formamide (HCONH ₂ ), acetamide (CH ₃ CONH ₂ ), dimethylformamide (HCON (CH ₃ ) ₂ ), dimethylacetamide (CH ₃ CON (CH ₃ ) ₂ ) or Benzamide (C ₆ H ₅ CONH ₂ ) and the like, but is not limited thereto.

On the other hand, these acid amides are mostly colorless and transparent liquids, and the lower amides are well soluble in water.

The metal amide may be, for example, but not limited to sodium amide (NaNH ₂ ) or calcium amide (Ca (NH ₂ ) ₂ ).

These metal amides are white solids, and when water is added, they generate ammonia and decompose.

In general, metal amides are produced by adding alkali metals, alkaline earth metals or their hydrogen compounds into liquid ammonia.

In addition, amides in which the amino group —NH ₂ is bonded to an acid group in the form of RCONH— are included in the amides. For example, CH ₃ CONH − is called acetamide, and is used in the present invention as described above. Suitable amides include all such kinds of amide compounds.

In the present invention, a sulfur polymer cement may be prepared by using amides as a sulfur modifier together with a dicyclopentadiene-based modifier.

That is, the sulfur polymer cement may be prepared by melting and mixing amides and dicyclopentadiene-based (DCPD) modifiers at 120 to 160 ° C. as sulfur and a sulfur modifier.

The addition ratio of the dicyclopentadiene-based modifier used as the sulfur modifier in the present invention is 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 1 to 30 parts by weight, particularly preferably 100 parts by weight of sulfur. Preferably it is 5-25 weight part, and the addition rate of an amide is 1-100 weight part with respect to 100 weight part of sulfur, Preferably it is 5-35 weight part.

In the present invention, the amount of dicyclopentadiene-based modifier added range is relatively small compared to the existing prior patents, especially Korean Patent Registration No. 10-0911659, to control the amount of addition of a wide range of dicyclopentadiene-based modifiers However, compared with the conventional sulfur polymer cement, not only the same effect but also more performance can be achieved.

Particularly, in the case of the conventional Korean Patent No. 10-0911659, the amount of the dicyclopentadiene-based modifier included in the sulfur polymer cement produced to dissolve the solid sulfur polymer cement in water of 100 ° C. or less is based on 100 parts by weight of sulfur. Since it should be more than 30 parts by weight, it is very difficult to control the quality of the produced sulfur polymer cement, it is difficult to ensure the homogeneity of the product.

In addition, the sulfur polymer cement of the present invention improves the hydrophobicity and increases the hydrophilicity of the sulfur polymer cement to improve the hydrophobicity such as emulsification, surface activity, and dispersion with water. The workability (workability) is improved, and the quality of the sulfur polymer cement, such as viscosity control and reaction suppression, can be expressed uniformly.

Therefore, in the case of a concrete product using a conventional sulfur polymer cement on the actual work site, problems such as securing the quality and stability of the concrete is not raised.

However, in the present invention, it is possible to control the addition amount of the dicyclopentadiene-based modifier in a wider range than the conventional Korean Patent No. 10-0911659, in particular, a smaller amount of dicyclopenta than the conventional Korean Patent No. 10-0911659. The addition of diene-based modifiers has made it possible to produce sulfur polymer cements exhibiting the same or better performance as in Korean Patent Registration No. 10-0911659.

In particular, high-quality stable sulfur polymers having excellent fluidity and workability while maintaining or exhibiting more physical properties, including properties of dissolving in water at 100 ° C. or lower, which are characteristics of Korean Patent Registration No. 10-0911659. It is possible to manufacture cement.

On the other hand, as the addition ratio of the dicyclopentadiene-based modifier increases, the viscosity continues to increase and the reaction control becomes difficult. Also, Korean Patent Registration No. 10-0911659 and other prior patents such as the United States and Japan have already occurred. As described.

Therefore, in the present invention, it is preferable that the addition ratio of the dicyclopentadiene-based modifier is determined in a comprehensive manner in consideration of various parts such as viscosity, reaction time, temperature control, and other conditions in manufacturing sulfur polymer cement. .

Dicyclopentadiene-based modifiers based on 100 parts by weight of sulfur in order to have a more suitable range of viscosity, to improve uniform quality and product stability, and to disperse sulfur polymer cement particles evenly and more evenly in water. Is 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 1 to 30 parts by weight, particularly preferably 5 to 25 parts by weight.

In the sulfur polymer cement according to the present invention, the final viscosity at 140 ° C. of the reaction product obtained immediately before the end of the reaction is in the range of 0.01 to 3.0 Pa · s, preferably in the range of 0.05 to 1.5 Pa · s, more preferably 0.08 to 0.5 Pa · s range. Here, it is well known that quality control by temperature control, such as thermal history management of products, is the most important factor in achieving this viscosity range.

This viscosity range is in the range of 0.01 to 100.0 Pa.s, preferably in the range of 0.1 to 10.0 Pa.s, as disclosed in Korean Patent No. 10-0911659, but 100 for the sulfur polymer cement disclosed in Korean Patent No. 10-0911659. Since it has a viscosity of at least about 10.0 Pa · s in order to dissolve at or below ℃, the sulfur polymer cement according to the present invention has a relatively low viscosity compared to this viscosity.

In particular, in the prior patents of the United States and Japan, the strength of civil engineering and construction materials using a binder produced when the final viscosity of sulfur polymer cement is less than 0.05 Pa · s when mixing with aggregate for producing concrete material using sulfur polymer cement When the final viscosity of sulfur polymer cement exceeds 1.2 Pa · s, it becomes difficult to stir and mix for civil engineering and construction materials production using binders produced. It is described that the sex is significantly worsened.

Therefore, for excellent agitation and mixing operations, the final viscosity measured at 140 ° C. set forth in the present invention may be a viscosity within a range that includes a range of viscosities equal to 0.08 to 0.5 Pa · s set forth in the prior patents, such as US and Japan. By expression, sulfur polymer cements in the viscosity range having excellent flowability and workability can be produced.

Also, when using amides, fluidity and workability such as emulsification, surface activity, and dispersion with water are higher than those of sulfur polymer cement using pyridine or alkyl amines, which are heterocyclic amines. (workability) and improves the quality of the sulfur polymer cement, such as viscosity control, reaction inhibition, and the like has the advantage.

In addition, the odor generation level of the sulfur polymer cement of the present invention is very weak compared to the serious odor generated when the pyridine is a heterocyclic amine.

Particularly, in the sulfur polymer cement production system of the present invention, vapor by vaporization of a modifier that generates odor is discharged to the outside through a manual valve or an automatic emergency valve, or a separate deodorizer is connected or generated using a deodorant. Significant odor of the resulting product can be removed.

On the other hand, the amides (amide) 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 inhibition or viscosity control, thereby changing the reaction conditions, viscosity of the reaction product, and cooling. Causes various physical property changes such as conditions and odor removal.

In particular, it is possible to produce a sulfur polymer cement exhibiting physical properties that can be melted again at a temperature of less than 100 ℃ due to the use of amides (amide).

In preparing a liquid sulfur polymer cement according to the present invention, in the melt mixing of sulfur, a dicyclopentadiene-based modifier and amides, the mixing order of each component is not particularly limited, but the following method Among them, it is preferable to select the method most suitable for the physical properties of the final product.

(a) First, a batch method in which a dicyclopentadiene-based modifier and an amide modifier are added together with molten sulfur in a batch method, mixed, heated and polymerized to react.

(b) Next, a method of preparing a liquid sulfur polymer cement by mixing a dicyclopentadiene-based modifier with sulfur, heating and polymerizing, followed by addition of an amide modifier and polymerization again. .

(c) Next, a dicyclopentadiene-based modifier and an amide modifier may be mixed, and then sulfur may be added and heated to polymerize to prepare a liquid sulfur polymer cement.

(d) Then, a method of preparing a liquid sulfur polymer cement may be obtained by mixing and heating a sulfur and an amide modifier, followed by polymerization to add a dicyclopentadiene-based modifier and then polymerizing again.

(e) Finally, dicyclopentadiene-based modifiers are mixed with sulfur, heated to polymerize, and then cooled to prepare a solid reaction product. The solid reaction product is melted again, and then amide modifier is added and heated to polymerize the reaction. It is possible to produce a liquid sulfur polymer cement.

Here, in the production method of sulfur polymer cement,

(a) In the case of the batch method, it is easy to control the conditions such as the type of the modifier, the reaction temperature, and the reaction time all at once at the most widely used method.

(b) is a method in which an amide modifier is added while sulfur and a dicyclopentadiene-based modifier are mixed, and a relatively small amount of amide modifier may be required compared to other methods.

The method (c) adds an amide modifier to the dicyclopentadiene-based modifier in advance to control the viscosity or suppress the reaction before the polymerization reaction, thereby controlling the rapid increase in the viscosity of the reactants and progressing the polymerization reaction smoothly. Reaction control can be facilitated.

Method (d) is a method of directly reacting with sulfur using an amide modifier, followed by adding and heating a dicyclopentadiene-based modifier to polymerize the reaction, as disclosed in Korean Patent No. 10-0911659. In addition, it was possible to find a tendency for the polymerization reaction to occur substantially even if amide (amide) modifier is directly reacted with sulfur.

The method (e) is a method of preparing a stabilized sulfur polymer cement and then remelting and reacting it.

The polymerization reactor used for melt mixing for the production of such a sulfur polymer cement can be used as long as it can be sufficiently mixed, it is preferable to use a hermetically sealed mixer mainly for liquid stirring.

On the other hand, as a result of the actual implementation of the above-described method of manufacturing the sulfur polymer cement, it is most preferable that the preparation by the method (b) requires a relatively small amount of addition of the amide modifier, and the control of the reaction is advantageous.

Hereinafter, a method of manufacturing a sulfur polymer cement according to a preferred embodiment of the present invention will be described with reference to FIG. 1 based on the method (b).

As shown in FIG. 1, in the method for preparing a sulfur polymer cement according to an exemplary embodiment of the present invention, sulfur and dicyclopentadiene-based modifier are first mixed (S100).

At this time, the temperature range for the polymerization reaction is to be made in the range of 120 ~ 160 ℃, preferably 125 ~ 140 ℃.

In this case, the mixing ratio of sulfur and dicyclopentadiene-based modifier is 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 1 to 30 parts by weight, particularly preferably 5 to 1 part by weight of sulfur. 25 parts by weight.

When sulfur and a dicyclopentadiene-based modifier are mixed, the temperature of the polymerization reactor is then increased to preferably in the range of 125 to 140 ° C., and an amide-type modifier is added to the polymerization reaction (S102).

Of course, it is also possible to maintain the temperature of the polymerization reactor without raising the temperature so that the polymerization reaction is carried out, but is not limited thereto.

The amide modifier added at this time is 1 to 100 parts by weight, preferably 5 to 35 parts by weight with respect to 100 parts by weight of sulfur.

On the other hand, the stirring speed of the polymerization reactor for mixing and polymerization reaction is 1 to 40 rpm, preferably 10 rpm.

And the polymerization reaction time may be made in the range of 120 ~ 200 minutes.

In the case of conventional sulfur polymer cements, the polymerization reaction had to be performed in the range of at least 180 minutes and at most 420 minutes, but in the present invention, the polymerization reaction time was also shortened by using amides as the sulfur modifier.

In addition, as described above, the stirring speed of the polymerization reactor can be significantly lowered in the course of the polymerization reaction as compared with the prior art. In the case of the sulfur polymer cement according to the present invention, the viscosity can be easily adjusted, and in particular, a sulfur polymer having a desired viscosity range. Cement can be prepared, it is possible to agitate at a relatively low stirring speed compared to the prior art.

When the polymerization reaction is completed, a liquid sulfur polymer cement is finally produced, and the solid sulfur polymer cement is cooled and solidified to prepare a solid sulfur polymer cement (S104).

On the other hand, in Japanese Unexamined Patent Publication No. 2003-277108 or Japanese Unexamined Patent Publication No. 2002-60491, molten sulfur is not easily reformed at 125 ° C or lower even when contacted with a sulfur modifier, and in the temperature range of 120 to 135 ° C. It is described that the polymerization reaction with the sulfur modifier is delayed, and there is no sudden exotherm and viscosity increase, but a slight temperature rise and a viscosity increase occur to maintain a constant viscosity.

It can be understood that the reaction temperature and reaction time in the present invention proceed similarly to the reaction conditions described in these prior patents, but the reaction in the present invention uses a new material called amide for the first time, and therefore, amides Viscosity, strength, hardness, stability, and odor specific amides of the final product according to the method and timing of the addition of (amide), the change in the amount of amide (amide), the vaporization conditions of the amide (amide), and Many differences occur in the ease of handling of the reaction product.

Taken together with the existing mechanisms, the present results show that the reaction between dicyclopentadiene-based modifier and sulfur is a kind of polymerization reaction, and melt mixing, which is a key process in the manufacturing process of sulfur polymer cement, is based on molten sulfur. It is a process for polymerizing sulfur by the polymerization reaction of a sulfur modifier and obtaining a sulfur polymer cement.

The sulfur reforming reaction includes an initial mixing reaction step in which molten sulfur and a sulfur modifier react to produce a sulfur polymer precursor precursor in which a ring of S ₈ sulfur is ring-opened and cyclized, Sulfur polymer precursor (precursor) and molten sulfur may be divided into a polymerization step in which molten sulfur is polymerized by continuously reacting by radical chain reaction due to the exothermic heat generated during precursor generation. .

In this reaction, the formation reaction of the sulfur polymer cement may be divided into an initial mixing reaction step showing an abrupt exothermic reaction and a polymerization reaction step showing an endothermic reaction, and the generation system of the sulfur polymer cement undergoes an endothermic reaction from an exothermic reaction as the polymerization reaction proceeds. Changes to

In addition, if the calorific value and the endothermic amount and the respective reaction time are different depending on the type of sulfur modifier or the amount of addition thereof, and the temperature control is not carried out correctly, the polymerization reaction may be congested and solidified.

Summarizing the results studied so far in the “sulfur-dicyclopentadiene-based modifier-amide modifier” system used in the present invention, the “sulfur-dish” may be achieved even when the amide-modifier is reacted with sulfur alone. As in the "clopentadiene-based modifier" system, it was confirmed that the polymerization reaction was carried out. As in the reaction mechanism in the "sulfur-dicyclopentadiene-based modifier" system, an exothermic reaction occurred in the initial mixing reaction step to allow the sulfur polymer cement precursor. The formation and continuous reaction resulted in a polymerization reaction to significantly improve the stabilization phenomenon in all physical properties such as viscosity, strength, hardness, and stability of the final product sulfur polymer cement.

Hereinafter, an embodiment of the sulfur polymer cement according to the present invention and a comparative example of the existing sulfur polymer cement will be described in detail with reference to the drawings.

On the other hand, these examples and comparative examples are only presented to more clearly understand the present invention, not intended to limit the scope of the present invention, the present invention is the scope of the technical spirit of the claims to be described later Will be decided within.

First, an embodiment of the sulfur polymer cement according to the present invention is a computer using a motor control center (MCC) panel according to the [Method and Apparatus for Manufacturing Sulfur Polymer Cement] of Korean Patent Application No. 10-0658441 as a solid sulfur polymer cement. By automatic control or manual control.

An embodiment of the production of sulfur polymer cement of the present invention using this production apparatus will be described briefly as follows. However, the production is not limited to this embodiment, and it is well known that the production of sulfur polymer cement according to the present invention can be made by various methods such as the above-mentioned method of producing sulfur polymer cement using the production system.

(a) First, industrial sulfur powder is put into a 100-liter sulfur melting tank, the temperature is raised to about 130 ° C. to sufficiently dissolve powder sulfur, and the sulfur melting tank is kept at about 120 ° C. and stored. At this time, the stirring speed of the stirrer during storage is to maintain about 5 rpm.

(b) Dicyclopentadiene-based (DCPD) is also added to a DCPD tank, heated and stored at a temperature of about 60 ° C.

(c) Another modifier used in the present invention, amides, is stored in a separate modifier storage tank. As the amides introduced at this time, dimethylacetamide (CH ₃ CON (CH ₃ ) ₂ ) was used as the acid amide.

In addition to the dimethyl acetamide, formamide (HCONH ₂ ), acetamide (CH ₃ CONH ₂ ), or dimethyl formamide (HCON (CH ₃ ) ₂ ) and the like were added to prepare sulfur polymer cement from each.

As the metal amides, sodium amide (NaNH ₂ ) or calcium amide (Ca (NH ₂ ) ₂ ), which are widely used for compound synthesis, was also added. In each case, the physical properties described later showed little difference and were similarly exhibited. .

(d) When each of the modifiers required for the production of sulfur polymer cement of the present invention is prepared, it is introduced into the polymerization reactor through a transfer line by a predetermined compounding amount. At this time, the molten sulfur and DCPD is gradually mixed to be pre-mixed through a static mixer which is a kind of line mixer installed in the transfer line to be introduced into the polymerization reactor. Here, molten sulfur is used for the flow meter and DCPD is transferred to the polymerization reactor by the required amount set using the metering pump.

(e) The polymerization reactor is maintained at a temperature at which the transferred molten sulfur does not solidify, and each component transferred to the polymerization reactor is gradually heated to about 130 ° C., which is necessary for the polymerization reaction, to perform the polymerization reaction. Here, an electric heater and a hydrocarbon oil were used as the heat medium oil for heating.

(f) At this time, stirring was performed at a speed of about 10 rpm while paying attention to a sudden temperature increase due to an exothermic reaction. The reaction product proceeds further for 10 to 20 minutes at the time when the color becomes thick in the transparent state of orange color (i.e., when the precursor starts to form), and when it turns into a translucent dark red color (sulfur polymer cement When the viscosity is increased), the amides are also slowly added to the polymerization reactor in the required amount through the metering pump.

(g) Measuring the viscosity of the sulfur polymer cement as the color turns to opaque dark brown as the polymerization reaction continues, terminating the polymerization reaction when the required viscosity is reached, and using the cooling device to melt the sulfur polymer cement. Was cooled to about 120 ° C. in a short time and discharged from the polymerization reactor to prepare a solid sulfur polymer cement.

The remelting temperature of the solid sulfur polymer cement produced in this way was 65 ~ 80 ℃.

Next, in order to compare the physical properties of the sulfur polymer cement according to the embodiment of the present invention and the sulfur polymer cement according to the comparative example of the prior art, the sulfur polymer cement produced by the prior patent and the sulfur produced by the present invention The remelting temperatures of polymer cements were compared and the results are shown in the following table.

 Comparison of Remelting Temperature of Sulfur Polymer Cement Patent Major modifiers Remelting Temperature Remarks Invention patent DCPD + amide 65 ~ 80 ℃ Melt below 100 ℃ Korean patent application
10-20090089325 DCPD + ammonium salt,
DCPD + Urea Compound 80 ~ 85 ℃ Melt below 100 ℃ Korean patent application
10-20090094414 DCPD + Amino Acid 85 ~ 90 ℃ Melt below 100 ℃ Korea registered patent
10-0911659 DCPD + heterocycle
Amines (pyridine) 80 ℃ Melt below 100 ℃ Korea registered patent
10-0632609 DCPD 120 DEG C Melt above 120 ℃ WO 030766360 DCPD 120 DEG C Melt above 120 ℃

In order to compare the liquid phase change of the test body according to the change of the remelting temperature of the solid-state sulfur polymer cement prepared in accordance with one preferred embodiment of the present invention, the solid-state sulfur polymer cement and the comparative example according to the embodiment of the present invention After each amount was put in a test tube, charged into a thermosel (Brookfield Viscometer System) heater with constant temperature, and the liquid phase change was observed at each temperature while changing the temperature from room temperature to 120 ° C. to 160 ° C. to room temperature. Is shown in FIG. 2.

As shown in FIG. 2, the sulfur polymer cement produced in the preferred embodiment of the present invention is remelted at 80 ° C. or lower to show a stable state without continuous phase separation even after the temperature is increased, and after cooling to room temperature Denotes the same solidified shape as the comparative example. At this time, the difference in solidification color, as can be seen in Figure 2 is due to the difference in the degree of modification of sulfur due to the difference in the mixing ratio of the modifier used.

On the other hand, the general sulfur polymer cement obtained in the comparative example does not generate remelting at all at 80 ° C., and remains solidified. As a result of the continuous temperature increase, the general sulfur polymer cement starts to melt at about 120 ° C. After cooling to room temperature, the solidified shape is similar to that of the sulfur polymer cement of the embodiment of the present invention.

As can be clearly seen from the experimental results, the sulfur polymer cement according to the present invention can be melted again at 100 ° C. or lower, whereas the general sulfur polymer cement was not melted at 100 ° C. or lower and melted at 120 ° C. or higher.

Therefore, using conventional sulfur polymer cement according to the existing foreign prior patents, the Portland cement concrete is mixed with hydraulic materials and aggregates by remelting in water below 100 ° C., which is the characteristic of the sulfur polymer cement of the present invention. You can see that the operation cannot be performed.

FIG. 3 is a photograph showing a phase change of a sulfur polymer cement at 160 ° C., which is a viscosity transition temperature of sulfur, and at room temperature after melting at 160 ° C. FIG.

As can be seen in Figure 3, the sulfur polymer cement of the embodiment according to the present invention, once the temperature starts to increase above the polymerization temperature of about 125 ℃, the polymerization starts to start again and accordingly the viscosity also begins to increase Above 145 ° C, the viscosity increased significantly.

Accordingly, the melt state of the sulfur polymer cement of the present invention and the melt state of the sulfur polymer cement of the comparative example are significantly different with the temperature change. Accordingly, it can be seen that the phase change at room temperature after melting at 160 ° C. also differs significantly between the sulfur polymer cement of the example according to the present invention and the sulfur polymer cement of the comparative example.

On the other hand, the results of comparing the hydrophilicity of the embodiment of the present invention and the comparative example of a conventional sulfur polymer cement can be confirmed through FIG.

An appropriate amount of the solid sulfur polymer cement produced in the embodiment of the present invention and an appropriate amount of the general sulfur polymer cement produced in the comparative example were charged in a test tube, respectively, and the test pieces were melted while gradually raising the temperature.

At this time, the test specimens of Example were melted at 80 ° C. or lower, and the comparative specimens were 120 ° C. or higher, and the change of the melt was observed while gradually adding 60 ° C. water to each of the melted test specimen melts. 4 is shown.

As can be seen in Figure 4, the sulfur polymer cement of the embodiment of the present invention in the molten state of 80 ℃ or less in contact with water at 60 ℃ does not produce a precipitate and maintained a molten liquid state without any change, but compared The sulfur polymer cement of the example has a remelting temperature of 120 ° C, so it can be seen that a precipitate forms when it comes into contact with water at 60 ° C. You will find that water vapor continues to rise upwards.

As can be seen from the comparative examples of the test results of the sulfur polymer cement according to the present invention and the conventional sulfur polymer cement described above, it can be seen that the sulfur polymer cement according to the present invention can be remelted at a temperature of 100 ° C. or less. .

In addition, sulfur polymer cement particles that are well dissolved and dissolved in water can be evenly dispersed, and in particular, the production of sulfur polymer cement of low viscosity is possible, so that when the sulfur polymer cement is used in actual construction structures and facilities, the quality can be uniformly expressed. It becomes possible.

It will be apparent to those skilled in the art that various modifications, additions and substitutions are possible, without departing from the spirit and scope of the invention as defined by the appended claims. And additions should be considered as falling within the scope of the following claims.

Claims (13)

brimstone; And
As the modifier of sulfur,
0.1 to 100 parts by weight of a dicyclopentadiene-based modifier based on 100 parts by weight of sulfur; And
Sulfur polymer cement, characterized in that 1 to 100 parts by weight of the amide modifier is melt-mixed with respect to 100 parts by weight of sulfur.
The method of claim 1,
Sulfur polymer cement, characterized in that the amide is at least one of acid amide and metal amide.
3. The method of claim 2,
The acid amide is formamide (HCONH ₂ ), acetamide (CH ₃ CONH ₂ ), dimethylformamide (HCON (CH ₃ ) ₂ ), dimethylacetamide (CH ₃ CON (CH ₃ ) ₂ ) and benzamide (C Sulfur polymer cement, characterized in that at least one of ₆ H ₅ CONH ₂ ).
3. The method of claim 2,
The metal amide is a sulfur polymer cement, characterized in that at least one of sodium amide (NaNH ₂ ) and calcium amide (Ca (NH ₂ ) ₂ ).
The method of claim 1,
The dicyclopentadiene-based modifier is a dicyclopentadiene (DCPD) monomer alone, or a mixture in which at least one of a cyclopentadiene (CPD) monomer, a DCPD derivative, and a CPD derivative is added to the DCPD monomer, or Cyclocyclic as a solvent in the dicyclopentadiene (DCPD) monomer alone or in a mixture in which at least one of a cyclopentadiene (CPD) monomer, a DCPD derivative, and a CPD derivative is added to the DCPD monomer. Dipentene, limonene, vinyltoluene, styrene, methylstyrene, dicyclopentene, pinen and indene are cyclic hydrocarbon compounds (indene) or aromatic hydrocarbon compounds (aromatic hydrocarbon compounds) characterized in that the olefin mixture (olefin) mixture added Sulfur polymer cement.
The method of claim 1,
The sulfur polymer cement is a sulfur polymer cement, characterized in that the liquid or solid.
A sulfur polymer cement production method, characterized in that sulfur polymer cement is produced by melting and mixing sulfur and a dicyclopentadiene modifier and an amide modifier as sulfur modifiers.
The method of claim 7, wherein
The dicyclopentadiene-based modifier is mixed in the range of 0.1 to 100 parts by weight based on 100 parts by weight of the sulfur,
The amide modifier is a method for producing a sulfur polymer cement, characterized in that mixing 1 to 100 parts by weight based on 100 parts by weight of the sulfur.
The method of claim 7, wherein
The amide is a method for producing a sulfur polymer cement, characterized in that at least one of acid amide and metal amide.
10. The method of claim 9,
The acid amide is formamide (HCONH ₂ ), acetamide (CH ₃ CONH ₂ ), dimethylformamide (HCON (CH ₃ ) ₂ ), dimethylacetamide (CH ₃ CON (CH ₃ ) ₂ ) and benzamide (C ₆ H ₅ CONH ₂ ) The method for producing a sulfur polymer cement, characterized in that at least one.
10. The method of claim 9,
The metal amide is a method of producing a sulfur polymer cement, characterized in that at least one of sodium amide (NaNH ₂ ) and calcium amide (Ca (NH ₂ ) ₂ ).
The method of claim 7, wherein
The dicyclopentadiene-based modifier is a dicyclopentadiene (DCPD) monomer alone, or a mixture in which at least one of a cyclopentadiene (CPD) monomer, a DCPD derivative, and a CPD derivative is added to the DCPD monomer, or Cyclocyclic as a solvent in the dicyclopentadiene (DCPD) monomer alone or in a mixture in which at least one of a cyclopentadiene (CPD) monomer, a DCPD derivative, and a CPD derivative is added to the DCPD monomer. Dipentene, limonene, vinyltoluene, styrene, methylstyrene, dicyclopentene, pinen and indene are cyclic hydrocarbon compounds (indene) or aromatic hydrocarbon compounds (aromatic hydrocarbon compounds) characterized in that the olefin mixture (olefin) mixture added Process for producing a sulfur polymer cement.
The method of claim 7, wherein
The melt mixing is a method of producing a sulfur polymer cement, characterized in that made in a temperature range of 120 ~ 160 ℃.

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