KR20040097611A - Performance-improving method of PET recycling polymer concrete to apply highly efficient nano particles - Google Patents

Abstract

PURPOSE: Provided is a production method of recycled polyester(pet) polymer concrete with heat resistance and water repellency by using recycled pet-based unsaturated polyester resin and high performance nanomaterials. CONSTITUTION: The recycled pet polymer concrete composition comprises the components of: 5-30wt.% of recycled pet-based unsaturated polyester resin as a binder; 5-30wt.% of filling material such as potassium bicarbonate or fly ash for good adhesive power due to increase of viscosity; 40-90wt.% of aggregate containing fine aggregate(0.074-5mm size) and coarse aggregate(5-50mm size); and 0.01-30wt.% of nanomaterials having a 0.01nanometer-100micrometer size, wherein the nanomaterials for heat-resistance are borides, carbides or nitrides of metal selected from the group consisting of Si, Al, Zr, Sc, La, Se, Nd, Y, etc. and the nanomaterials for water repellency are F, SiO2, etc. The composition is produced by mixing the above materials and curing mixtures at room temperature(17-23deg.C) or 50-2000deg.C over 24hrs.

Description

Performance-improving method of PET recycling polymer concrete to apply highly efficient nano particles

The present invention relates to a PET recycled polymer concrete using a high-performance nanomaterials and a method for manufacturing the same, specifically, by using waste PET regenerative unsaturated polyester resin to obtain resources recycling, environmental conservation and economic benefits, To improve the fire-heat resistance and hydrophobic-water repellency.

In general, there are three methods for producing polymer concrete.

The first method is PCC (Polymerized concrete), which supplements the strength by adding organic polymer to the existing Portland cement binder. This method consists of a structure that protects the interior by forming a polymer film layer on the cement layer at the same time as the hydration of the cement by mixing the emulsified particles, polymer powder or monomer thereof that can be dispersed with the cement binder and water.

The second method is PC (Polymer concrete) using pure polymer as a binder of aggregate. Since this method uses a polymer as a binder, it is generally evaluated to be superior in strength, adhesion, durability, weather resistance, and chemical resistance to concrete.

The third method is PIC (Polymer Impergnated Concrete) in which concrete material made of hardened cement is impregnated with polymer monomer, but it is not used well because it is difficult and expensive in practical application.

Since the polymer concrete is used as a binder instead of cement, the polymer concrete is not easily penetrated by moisture or air, and thus has excellent durability against the external environment. It is known to have better compressive and flexural strength than cement concrete. Therefore, it can be used for the manufacture of communication manholes or radioactive waste containers requiring long-term durability, and it is also used for repairing bridges, highways and parking lots made of ordinary concrete. However, since the unsaturated polyester resin is used as the polymer resin, the problem of deterioration of mechanical properties due to temperature rise was inevitable.

As described above, the conventional polymer concrete has excellent mechanical properties such as strength. However, since unsaturated polyester resin is used, there is a problem that the mechanical properties decrease due to the temperature rise and the economical efficiency of the resin is poor. .

In addition, the conventional polymer concrete has been raised a problem that the production cost is basically reflected in the consumer price.

Most synthetic polymers are flammable and are likely to release toxic gases on combustion. Therefore, for a long time, efforts have been made to impart flame retardancy and nonflammability with the development of synthetic resins. In particular, the flame retardant grades of synthetic resins used as exterior materials for electrical and electronic products are regulated by law in most countries.

There has been a technique of using a halogen compound such as chlorine or bromine as a flame retardant. However, since halogen compounds emit various environmental pollutants and human hazards such as dioxin and furan during a fire, various regulations on existing halogen flame retardants have been strengthened. There is an increasing demand for environmentally friendly non-halogen flame retardants. Moreover, since the use of antimony lowers the thermal stability and weather resistance of the plastic, there is a disadvantage in that physical properties deteriorate rapidly during the stay in the injection molding machine.

In order to supplement the above problems, a phosphorus flame retardant such as a phosphate ester compound is used in plastic molding, but this has a problem in that the surface of the molded product tends to be poor and the heat resistance is lowered. In particular, when left at a high temperature for a long time, the decomposed phosphate ester compound is further reduced to phosphoric acid, etc., so that the physical properties of the molded product may be drastically lowered. This change is particularly acute in the case of phosphate esters in oligomeric form. Most phosphorus compounds have a liquid or low softening point, and when added to a synthetic resin, they act as plasticizers or softeners. In addition, in the thermoplastic resin such as ABS, PP or PE, or the thermosetting resin such as phenol resin, UPE or epoxy, the glass transition point is lowered or moved to lower the heat deformation temperature or heat resistance. Therefore, when the phosphorus compound is added to the resin in order to impart flame retardancy to the resin, there is a problem that the physical properties of the resin are lowered. In particular, in products requiring high modulus and strength, it is difficult to satisfy desired physical properties as existing phosphorus compounds. Therefore, the phosphorus-based flame retardant does not effectively act to improve the flame resistance and heat resistance of the final resin. For these reasons, there is an urgent need for an effective technology for imparting flame retardancy while maintaining stable physical properties of resins without using harmful halogen compounds.

Nano-materials are capable of atomic manipulation of 10 ^-9 m level, and when these nano-phase materials are added to other materials, they can form microstructures that cannot be realized with conventional materials. The present invention is made possible to realize better unit performance and to improve the durability of polymer concrete such as fire resistance, heat resistance and hydrophobicity, water repellency by using nano material suitable for the purpose by utilizing these properties of nano material. Was completed.

Refractory-heat-resistant materials (silicon, alumina, zirconium, scandium, lanthanum, cerium, neodium, yttrium, titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten and mixtures thereof; Particles characterized by nanomaterializing water, carbide or nitride)

Hydrophobic-water-repellent material (particles characterized by nanomaterials such as fluorine and silica)

The present inventors have proposed a method for producing polymer concrete having excellent fire resistance and heat resistance performance by applying high-performance nanomaterials to supplement waste problems by recycling waste PET using binder unsaturated unsaturated resin.

It is an object of the present invention to provide a new polymer concrete composition.

It is also an object of the present invention to provide an inexpensive polymer concrete having excellent durability, such as refractory-heat resistance and hydrophobic-water repellency, and a manufacturing method thereof, using the composition.

In order to achieve the above object, the present invention provides a polymer concrete composition comprising a waste PET regenerated unsaturated polyester resin and a high-performance nanomaterial (0.01nm-100㎛).

In another aspect, the present invention provides a polymer concrete prepared by the composition and a method for producing the same.

Hereinafter, the present invention will be described in detail.

The polymer concrete composition according to the present invention is characterized by containing a waste PET regenerated unsaturated polyester resin and a high performance nanomaterial. In the conventional polymer concrete, a thermoplastic resin was used, but mechanical properties such as strength were poor, and there was a problem in that curing shrinkage occurred. On the other hand, in the present invention, the mechanical properties of polymer concrete are improved by using waste PET regenerated unsaturated polyester resin, which is a thermosetting resin. In addition, by using the high-performance nanomaterials according to the present invention, the fire-resistance and heat-repellent performance of the existing general polymer concrete were improved.

Specifically, 5-30% by weight of waste PET regenerated unsaturated polyester resin, 40-90% by weight aggregate, 5-30% by weight filler and 0.01-30% by weight high-performance nanomaterial, and the initiator (catalyst) for the total amount of resin were 0.1-5.0 It is preferably composed of%.

The curing method is preferably performed at room temperature curing (20 ± 3 ℃) and high temperature curing (curing for 24 hours or more at 50 ~ 200 ℃).

If the content of the resin is too small, it is preferable to add the composition ratio as described above, since the bonding strength between particles may be weakened and the strength may be lowered accordingly.

If the filler is not included at all, it may be a problem in the development of strength when preparing the cured product using the composition, but it is preferable to add it, but not more than 50% of the total weight, in the present invention calcium bicarbonate or fly ash Preference is given to adding 5-30%.

The thermosetting polymer resin used in the polymer concrete composition according to the present invention refers to waste PET recycled unsaturated polyester resin, which is made of recycled waste PET to make unsaturated polyester resin, and used for the production of resin. PET pieces are usually obtained from drinking water bottles. At this time, several middle class patent components are added to give flexibility or rigidity.

Generally, polymer resins such as epoxy resins, polyurethane resins, acrylate resins and unsaturated polyester resins are used for polymer concrete. Epoxy resin is difficult to control the hardening behavior, but it is difficult to manufacture concrete, but it has advantages such as low shrinkage rate and strong bonding strength with the aggregate. Polyurethane is not easy to control the curing reaction because it is bonded through a condensation reaction like epoxy resin. On the other hand, since the acrylate resin or the unsaturated polyester resin is cured through a radical reaction, the solidification can be easily controlled. In particular, acrylate resins are highly volatile and may not have sufficient binding strength with aggregates, but since they mainly use methyl methacrylate (methyl methacrylate, MMA) as a monomer, they can be easily mixed with aggregates due to their low viscosity. Unsaturated polyester is the most widely used material as a polymer concrete binder, and has the advantage of good binding strength and high molecular weight. The polymer resin, such as a liquid unsaturated polyester, contains a plurality of unreacted double bonds in one molecule, and this part induces curing while undergoing a radical reaction. In addition to the unsaturated polyester, styrene monomer can be added to the inside of the resin as a diluent to lower the viscosity of the resin, thereby improving workability and controlling the degree of crosslinking.

The use of aggregate in polymer concrete is the same as in normal cement concrete. However, when the hydrophilic aggregate absorbs moisture, in the polymer concrete, a water film is formed between the binder layer surrounding the aggregate and the aggregate surface, thereby weakening the adhesive strength between the binder and the aggregate, so that the strength is lowered. Therefore, it is necessary to dry the water content to 0.3% or less. . In the polymer concrete composition according to the present invention, the aggregate is 0.074 to 5 mm and the coarse aggregate is used to be 5 to 50 mm.

The filler is a particulate filler for the purpose of reducing the amount of resin used per unit volume and increasing the viscosity to increase the adhesion. In order to reduce the viscosity, spherical inert fine particles are advantageous, but in terms of increase in size, irregular shapes are more advantageous in that the specific surface area is larger.

The high-performance nanomaterials of the present invention can be used in all of the above-mentioned material surfaces having fire-heat resistance and hydrophobic-water repellency, and are generally fine powder (0.01 nm-100 μm) and liquid phase. Preferably, the refractory-heat-resistant nanomaterials include silica, alumina, zirconia, scandium, and the like, and the hydrophobic-hydrophobic nanomaterials include nanomaterials such as fluorine series and silica.

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

However, the following examples are illustrative of the present invention, and the content of the present invention is not limited by the examples.

(Examples 1 to 11) Fabrication and Characteristics of Waste PET Recycled Polymer Concrete Using High-Performance Nanomaterials

By mixing the polymer concrete composition of the composition ratio as shown in Table 1 and Table 3 to prepare a polymer concrete using waste PET regenerative unsaturated polyester.

Molding molds were produced using an aluminum mold (diameter 75 mm, length 150 mm). After the test, each of the cured test pieces was heated to 20 ° C. to 1000 ° C. to confirm mechanical properties such as strength.

As the binder resin, waste PET regenerated unsaturated polyester resin was used, sand was used silica sand having a diameter of 0.2 to 0.6 mm, and calcium carbonate powder was used as a filler.

Refractory-heat-resistant nanomaterials were used as zirconia powder, and hydrophobic-water-repellent nanomaterials were used as fluorine powder. Zirconia is a material known as an effective material as a fire retardant, and fluorine is a material known as an effective material for hydrophobicity.

Methyl ethyl ketone peroxide (MEKPO) was used as a curing agent and cobalt octoate (Cobalt Octoate) was used as a curing accelerator. In all the examples below, the materials and molds used are as mentioned above unless otherwise specified.

Each material was weighed and weighed up to 0.5% of the weight per batch. It was also mixed using a batch mixer. Wax was used as a release agent and compaction was performed using an external vibrator.

[Table 1] Polymer Concrete Composition with Fire-Resistant Performance Nanomaterials

Example Number Resin (UPE) (5-30%) Filler (calcium bicarbonate) (5-30%) Aggregate (40-90%) Nano material (0.01-30%) Coarse aggregate Fine aggregate Fire-Resistant Performance Materials (Zirconia) One 11 11 39 39 0 2 11 11 36.5 36.5 5 3 11 11 34 34 10 4 11 11 31.5 31.5 15 5 11 11 29 29 20 6 13 13 27 27 20 7 15 15 25 25 20

Experimental Example 1 Measurement of Compressive Strength According to Heating Temperature

The intensity | strength was measured about the test body produced in Examples 1-4. The fabricated specimens were cured at room temperature (20 ± 3 ℃) and high temperature (cured at 100 ℃ for more than 24 hours). Unlike general cement concrete, polymer concrete has good roughness. Compressive strength was measured after heating to the temperature of [Table 2].

In the compression test, five specimens were loaded in a UTM (compression tester) so that the loading speed was 2.5kgf / cm2 per second, and the load at break was measured. The size was divided by the cross section of the specimen to calculate and average the compressive strength.

The results are shown in Table 2 below.

[Table 2] Compressive strength according to heating temperature

Example Number Compressive strength (kg / ㎠) 20 ℃ 60 ℃ 100 ℃ 300 ℃ 500 ℃ 700 ℃ 1000 ℃ Room temperature curing High temperature curing Room temperature curing High temperature curing Room temperature curing High temperature curing Room temperature curing High temperature curing Room temperature curing High temperature curing Room temperature curing High temperature curing Room temperature curing High temperature curing One 825 907 541 595 172 189 80 88 35 38 12 13 5 5 2 831 914 786 865 747 822 612 684 456 528 298 347 34 38 3 838 922 793 872 754 829 675 730 548 595 327 355 64 76 4 847 932 821 903 805 886 767 828 649 695 430 486 106 134 5 851 936 849 934 842 926 808 889 688 752 402 467 137 165 6 886 975 867 954 841 925 804 868 674 721 463 476 98 123 7 901 991 784 862 811 892 724 801 593 645 379 400 87 115

(1) Effect of adding refractory-heat-resistant nanomaterials (Examples 1 to 5)

In the case of Example 1, the nanomaterial is not included, the cured product produced a sharp decrease in compressive strength as the temperature increases, and as shown in Examples 2 to 5 including the nanomaterial, the polymer concrete cured product according to the present invention It is shown that the heat-resistance performance is much better than that of general polymer concrete, and that the fire-resistance performance is better than that of general cement concrete.

(2) Influence by the resin amount change of the polymer concrete composition (Examples 6-7)

As can be seen in Examples 5 to 7, the compressive strength at room temperature increased as the amount of resin increased, but as can be seen from [Table 2], it can be seen that the fire-resistant performance decreases as the amount of resin increases. As the amount of resin increases, it can be seen that the refractory-heat-resistant nanomaterial should also increase.

TABLE 3 Polymer concrete compositions and results with hydrophobic-water repellent nanomaterials

Example Number Resin (UPE) (5-30%) Filling material (calcium bicarbonate or fly ash) (5-30%) Aggregate (40-90%) Nano material (0.01-30%) Contact angle (°) Coarse aggregate Fine aggregate Water-Repellent Performance Improvement Material (Fluorine) 8 11 11 39 39 0 10 ° 9 11 11 31.5 31.5 5 8 ° 10 11 11 34 34 10 7 ° 11 11 11 29 29 20 5 °

(3) Effect of adding hydrophobic-water repellent nanomaterials (Examples 8 to 11)

This example measures the contact angle between water and polymer concrete by dropping water on the specimen.

In the case of Example 8, the nanomaterial was not included it was confirmed that the contact angle with the water came out about 10 °.

On the other hand, in Examples 9 to 11 including nanomaterials, the prepared cured product was found to decrease the contact angle with water as the amount of nanomaterial added increased. It can be seen that.

As described above, the polymer concrete according to the present invention does not deteriorate in mechanical properties as compared to polymer concrete using a general unsaturated polyester resin, it is economically excellent. In addition, since the addition of nanomaterials has better fire-resistance performance than general polymer concrete, the problem of deterioration of mechanical properties due to heat, which has been pointed out as a problem in general polymer concrete, has been solved. In addition, hydrophobic and water-repellent performance is improved, and the thermal conductivity is small, the heat insulation effect is excellent. Therefore, the polymer concrete according to the present invention can be used as a general structural material, and when used as a building structural material can significantly lower the requirements of the refractory-heat-resistant material and waterproof material additionally installed in addition to the structural material.

Claims (9)

Polymer concrete composition consisting of waste PET regenerated unsaturated polyester resin 5-30% by weight, filler 5-30% by weight, aggregate 40-90% by weight, fire-resistant heat-resistant nanomaterial 0.01-30% The method of claim 1, wherein the refractory-heat-resistant nanomaterial is silica, alumina, zirconium, scandium, lanthanum, cerium, neodium, yttrium, titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten and mixtures thereof. Polymer concrete composition, characterized in that the nano-materialized material having a refractory-heat resistance, such as metal bead, carbide, or nitride selected from the group consisting of Polymer concrete composition consisting of waste PET regenerated unsaturated polyester resin 5-30 wt%, filler 5-30 wt%, aggregate 40-90 wt%, hydrophobic-water repellent nanomaterial 0.01-30% The polymer concrete composition according to claim 1, wherein the hydrophobic water-repellent nanomaterial is nanomaterialized of a hydrophobic-water repellent material such as fluorine and silica. The polymer concrete composition according to claim 2 or 4, wherein the nanomaterial has a size of 0.01 nm to 100 µm. The polymer concrete composition according to claim 1 or 3, wherein the binder uses waste PET regenerated unsaturated polyester resin. 4. The polymer concrete composition according to claim 1 or 3, wherein the filler is calcium bicarbonate and fly ash. The polymer concrete composition according to claim 1 or 3, wherein the fine aggregate is 0.1 to 1.0 mm. The method for producing polymer concrete according to claim 1 or 3, wherein the polymer concrete composition is cured at room temperature (20 ± 3 ° C.) or at 50 to 200 ° C. for at least 24 hours.