KR20150070669A - Modified Sulfur Polymner Binder And Preparation Method Thereof - Google Patents

Abstract

The present invention relates to a method for preparing modified sulfur polymeric binders. The method includes: a first step of mixing dicyclopentadiene and an emulsifier; a second step of mixing asphalt with the mixture of the dicyclopentadiene and emulsifier; a third step of mixing molten sulfur with the mixture prepared in the second step; and a fourth step of initiating the reaction of the mixture prepared in the third step to modify the sulfur polymeric binders.

Description

Technical Field [0001] The present invention relates to a modified sulfur polymer binder and a method for producing the modified sulfur polymer binder.

The present invention relates to a modified sulfur binder and a process for producing the same. More particularly, the present invention relates to dicyclopentadiene (DCPD) and a sulfur binder modified with asphalt, and a process for producing the same.

In recent years, sewage pipes, manholes, and the like have been generally made of concrete. Instead of such general concrete, a so-called sulfur concrete having an aggregate bonded with a sulfur binder has been used to form sewage pipes, sidewalk blocks, It manufactures a variety of sulfur concrete structures such as shore blocks, reinforced soil blocks, manholes, sofa blocks, railway sleepers, u pipes, tiles and panels.

These sulfur binders are usually modified and used without using sulfur, one of which is a sulfur polymer binder modified with dicyclopentadiene (DCPD). Such dicyclopentadiene modified sulfur polymer binders are disclosed in Japanese Patent Application Laid-Open Nos. 2-25929 and 2-28529.

Modification by dicyclopentadiene (DCPD) is a kind of polymerization reaction, and the reaction mechanism associated therewith is described in U.S. Patent No. 4,311,826. During the preparation of the modified sulfur, the reaction of dicaclopentadiene with sulfur is initiated at the beginning of the reaction, and then the sulfur is polymerized by the radical chain reaction. It is also called a modified sulfur polymer binder (SPB).

Korean Patent Laid-Open No. 10-2012-0096385 uses alkyl amines and dicyclopentadiene together as modifiers.

When the sulfur polymer binder is mixed with the aggregate by using the modified sulfur polymer binder, a certain degree of compressive strength can be obtained, but the tensile strength is low and cracks are generated.

Korean Patent Publication No. 10-2012-0096385 Japanese Patent Application Laid-Open No. 25929/1989 Japanese Patent Laid-Open No. 2-28529

Accordingly, an object of the present invention is to provide a modified sulfur polymer binder which can obtain excellent tensile strength and bending strength at the time of molding into a structure.

The inventors of the present invention have found that a binder excellent in tensile strength at the time of molding of a structure can be obtained by using asphalt as a modifier together with dicyclopentadiene at the time of modification of a sulfur polymer binder.

The method for producing a modified sulfur polymer binder of the present invention comprises a first step of mixing dicyclopentadiene and an emulsifier, a second step of mixing a mixture of dicyclopentadiene and an emulsifier with asphalt, A third step of mixing the molten sulfur and the third step; And a fourth step of reacting and mixing the mixed mixture in the third step.

By using asphalt as a modifier together with dicyclopentadiene, a structure excellent in tensile strength and bending strength can be obtained when a sulfur concrete is formed and a structure is formed. Also, the economical efficiency is also excellent by using asphalt which is inexpensive.

When the sulfur polymer binder is modified, 0.01 to 200 parts by weight, preferably 0.1 to 10 parts by weight, and particularly preferably 1 to 5 parts by weight, of dicyclopentadiene may be used per 100 parts by weight of sulfur. The asphalt may be used in an amount of 0.01 to 400 parts by weight, preferably 0.1 to 20 parts by weight, per 100 parts by weight of sulfur.

When preparing the modified sulfur polymer binder of the present invention, the dicyclopentadiene and the emulsifier are first mixed, and the mixture of the dicyclopentadiene and the emulsifier is mixed again with the asphalt. The sulfur is preliminarily melted and finally mixed with the mixture to allow the polymerization reaction to proceed, thereby modifying it. The amount of emulsifier is used in an amount of 0.00001 to 10 parts by weight based on 100 parts by weight of sulfur.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1

1 kg of industrial sulfur was charged into the reactor to melt the sulfur at about 130 to 140 degrees Celsius. In a separate reactor, 5 g of emulsifier was mixed with 15 g of dicyclopentadiene (purity 85%, industrial grade). 15 g of asphalt was added thereto. The mixture was gradually added to a reactor in which sulfur was melted to carry out the reaction. When the color of the reaction mixture changed to dark, the reaction was terminated and the mixture was cooled at room temperature to prepare a modified sulfur polymer binder.

Example 2

1 kg of industrial sulfur was charged into the reactor to melt the sulfur at about 130 to 140 degrees Celsius. In an additional reactor, 5 g of emulsifier was mixed with 10 g of dicyclopentadiene (purity 85%, industrial grade). 20 g of asphalt was added thereto. The mixture was gradually added to a reactor in which sulfur was melted to carry out the reaction. When the color of the reaction mixture changed to dark, the reaction was terminated and the mixture was cooled at room temperature to prepare a modified sulfur polymer binder.

Comparative Example 1

300 g of industrial sulfur was charged into the reactor to melt the sulfur at about 130 to 140 degrees Celsius. 30 g of dicyclopentadiene (purity 85%, industrial grade) was added while stirring the reactor impeller. The mixture was gradually added to a reactor in which sulfur was melted to carry out the reaction. When the color of the reaction mixture changed to dark, the reaction was terminated and the mixture was cooled at room temperature to prepare a modified sulfur polymer binder.

Test Example

580 g of fly ash was added to 1080 g of each of the binders of the examples and the comparative examples, 3066 g of gravel and 1314 g of sand were charged and mixed using a blender for about 10 minutes. The mixture was molded in a mold and cooled in air to prepare a specimen. The tensile strength and flexural strength of each specimen were measured and reported in Table 1.

Flexural Strength (Mpa) Tensile Strength (Mpa) 1 day 7 days 30 days 30 days Example 1 8.3 14.0 14.6 9.9 Example 2 10.7 14.3 15.8 11.2 Comparative Example 1 7.8 9.8 10.3 5.9

* Bending strength is tested according to KS F2408.

** Tensile strength was measured by placing the specimen on the platen without eccentricity, applying load at 7 ~ 14kg / ㎠ per minute in the up and down direction, and reading the maximum load.

Claims (4)

A first step of mixing dicyclopentadiene and an emulsifier, a second step of mixing a mixture of dicyclopentadiene and an emulsifier with asphalt, a third step of mixing molten sulfur with the mixture mixed in the second step, And a fourth step of reacting the mixture mixed in the third step and reforming the modified mixture. The modified sulfur polymer according to claim 1, wherein the asphalt is used in an amount of 0.01 to 400 parts by weight, the dicyclopentadiene is used in an amount of 0.01 to 200 parts by weight, and the emulsifier is used in an amount of 0.00001 to 10 parts by weight per 100 parts by weight of sulfur. ≪ / RTI > Asphaltene and dicyclopentadiene modified sulfur polymer binder. The sulfur polymer binder according to claim 3, wherein the sulfur, asphalt and dicyclopentadiene have a weight ratio of 50 to 99.8: 0.1 to 25: 0.1 to 25.