KR100394465B1 - A binder composition comprising waste expanded polystyrene solution, a polymer composite material using it and a method for preparing a hardened product - Google Patents

Abstract

The present invention relates to a binder composition for polymer composites comprising an expanded expanded polystyrene (EPS) solution, more specifically, to an expanded polystyrene, styrene monomer or methyl methacrylate as reactive solvent and trimethylpropane trimethacryl as crosslinking agent. A binder composition for a polymer composite material having a rate as a main component and a coupling agent, a polymerization initiator and / or a polymerization accelerator as an auxiliary component, a polymer composite material comprising the same, and a method for producing a cured composite material therefrom.

Since the polymer composite material containing the binder composition of the present invention uses waste foamed polystyrene, which is generated as a large amount of waste, the manufacturing cost is much lower than that of the conventional polymer composite material containing the polymer synthetic resin as a binder, and the waste is recycled. It provides an excellent environmental protection effect to prevent secondary pollution in the process, and the cured composite material manufactured using the same has excellent performances corresponding to existing composite materials in terms of physical performance such as bending strength and compressive strength. It is a breakthrough product that can replace polymer composite materials.

Description

A binder composition comprising waste expanded polystyrene solution, a polymer composite material using it and a method for preparing a hardened product}

The present invention relates to a binder composition for a polymer composite material containing an expanded expanded polystyrene (EPS) solution, more specifically, a polymer such as polymer concrete or polymer mortar, which is currently being developed and used as a new material for construction and repair in the civil engineering and building field. As a binder component of a composite material, the present invention relates to a novel binder composition for composite materials, which recycles and uses waste foamed polystyrene that has been disposed of in large quantities after use, a polymer composite material comprising the same, and a method for producing a cured composite material therefrom.

Recently, with the development of the industry, the generation of various wastes is rapidly increasing, but most of the wastes are simply processed by landfilling and incineration, so there are various serious problems caused by environmental pollution in addition to waste of resources. have.

Among them, expanded polystyrene is a kind of synthetic resin composed of 98% air and 2% polystyrene, and it is widely used for cushioning materials and insulation packaging materials with excellent properties such as moisture resistance, buffer resistance, heat insulation, and economic efficiency. However, since most of the materials are used as wastes, they have various problems with their disposal. At present, the amount of waste polystyrene produced in Korea is increasing to 49,896 tons per year, and most of it is discarded through landfilling or incineration, and the recycling rate is 48.8% (1999, Styropol, Korea). As it is reported that it is only a degree, the effective post-treatment such as recycling is inevitably necessary to prevent environmental pollution of rivers and soils in consideration of the non-decomposable properties of expanded polystyrene.

Currently implemented for recycling waste foamed polystyrene, the foamed polystyrene is once crushed and the crushed product is mixed with cement to be recycled as a lightweight building material, or melted with heat or solvent, and then injection molded to form a case of a video cassette. Alternatively, there are a method of reproducing with a picture frame or the like, emulsification, solid fuelization, use of heat energy by combustion, and reuse of the raw material of expanded styropol again.

The recycling of waste foamed polystyrene is being promoted based on the recycling of raw materials rather than solid fueling or heat recovery due to environmental load. At present, heat reduction and solvent reduction methods are used for the reduction and recovery of waste foamed polystyrene as a raw material for recycling. However, in the case of thermal sensitization by directly heating and dissolving polystyrene, there are problems such as deterioration of recovered polystyrene, energy consumption, and inefficient transportation system, and limonene (for example, d- In the case of solvent reduction, which is deposited and dissolved in limonene), the cost of the solvent used is high, and in order to use the waste foamed polystyrene solution for the original purpose of polystyrene, there is a problem that a separate pretreatment process such as solvent separation is required after the reduction. Therefore, in order to recycle waste foamed polystyrene, it is required to develop an efficient recycling system with low environmental load and energy consumption and a recycling use.

On the other hand, polymer composite materials such as polymer concrete and mortar using thermosetting resins or thermoplastic resins, which are organic synthetic polymers as binders, have fast curing times, and have high strength characteristics such as bending strength, compressive strength, and tensile strength. While excellent in chemical resistance, resistance to freeze-thawing, abrasion resistance, and water resistance, they also have superior advantages over ordinary cement products such as cement concrete and mortar. It is widely used as a highly functional new material for foundation and artificial marble.

However, polymer composite materials such as polymer concrete and mortar, which are currently used, use organic synthetic polymers as binders in spite of various advantages as described above. Therefore, the production cost is relatively expensive compared to portland cement concrete or mortar products. Since it has to be committed, it is very limited in its scope of use and popularization.

Accordingly, the present invention is to solve the problems of the conventional polymer composite material described above, and by using the waste foamed polystyrene solution as a binder component of the polymer composite material for construction materials, new waste foamed polystyrene currently generated as environmental waste At the same time, it provides a recycling solution, and is a new binder for polymer composite materials, which is cheaper than conventional polymer composite materials and has a corresponding physical and chemical performance, and does not require a separate pretreatment process such as solvent separation. The purpose is to provide a composition.

The binder composition for a polymer composite material of the present invention for achieving the above object is characterized in that it comprises a waste foamed polystyrene solution and trimethylpropane trimethacrylate.

More specifically, the binder composition of the present invention comprises 1 to 50% by weight of waste expanded polystyrene (EPS), 45 to 94% by weight of styrene monomer (SM) or methyl methacrylate (MMA) and a crosslinking agent as a reactive solvent. 4 to 50% by weight of trimethylpropane trimethacrylate (TMPTMA) as a main component.

The binder composition is prepared by dissolving waste foamed polystyrene in the above-described content in a dissolution tank containing styrene monomer or methyl methacrylate, and then adding and mixing trimethylpropane methacrylate.

In addition to the above-described main components, the present invention may also include various conventional auxiliary components such as coupling agents, polymerization initiators, and polymerization promoters necessary for the polymer composite material to cure under suitable conditions.

The coupling agent is used to help the binder composition of the present invention to adhere to other inorganic material components such as aggregates and fillers. In the composition of the present invention, a silane compound such as γ-methacryloxy Propyltrimethoxy silane is used in an amount of 0.01 to 1.5 Phr, preferably 1 Phr.

In the above-mentioned content description, Phr (Parts per hundred parts of resin) is a hundred parts by weight of the sum of the waste expanded polystyrene, styrene monomer or methyl methacrylate and trimethylpropane trimethacrylate main components constituting the binder composition It means parts by weight.

In addition, the polymerization initiator and the polymerization promoter are used to generate radicals necessary for inducing various polymer polymerization reactions when the binder is cured. The polymerization initiator is used in the composition of the present invention in an amount of 0.5 to 3 Phr, preferably 2 Phr and the polymerization promoter. Is contained in an amount of 0.01 to 2 Phr, preferably 0.5 Phr.

The polymerization initiator may be appropriately selected and used organic peroxides commonly used in the art, and examples of the organic peroxides that may be used include benzoyl peroxide, lauroyl peroxide, and bisperoxide.

As the polymerization accelerator, N, N-dimethyl-p-toluidine (DMT) or N, N-dimethylaniline (DMA) is used. In using the polymer composite material containing the binder composition of the present invention, in the case of heating and curing under curing conditions, active radicals are generated by thermal decomposition of the polymerization initiator, so that a polymerization initiation reaction occurs, so that N, N-dimethyl- There is no need to add a separate polymerization promoter such as p-toluidine or N, N-dimethylaniline.

The present invention also relates to a polymer composite material comprising the above binder composition together with the aggregate and the filler.

In addition, according to the present invention, there is provided a method for producing a cured composite material by mixing and non-beaming the above-described polymer composite material, molding into a predetermined shape and size, and curing the mixture at room temperature and / or by heating.

The configuration of the present invention using the waste expanded polystyrene solution as a binder will be described with reference to the preparation of the polymer composite material composition.

First, a predetermined amount of waste foamed polystyrene is added to a dissolution tank containing styrene monomer or methyl methacrylate to dissolve, and the solution is cooled to room temperature. When trimethyllopropane trimethacrylate which is a crosslinking agent is mixed with the cooled solution, the production of the binder composition for the polymer composite material containing the waste expanded polystyrene solution as a main component is completed.

After adding a silane as an auxiliary component, an organic peroxide as a polymerization initiator, and N, N-dimethyl-p-toluidine or N, N-dimethylaniline as a polymerization accelerator, a conventional method for producing polymer concrete and mortar According to the present invention, the aggregate and the filling material are added to the beam and molded into a predetermined shape and size using a mold mold, and then cured and / or heated (65 to 80 ° C.) for 5 to 7 days at room temperature (20 ° C.). Curing for hours to 24 hours yields a cured composite material.

Hereinafter, each component constituting the binder composition and the polymer composite material of the present invention will be described in more detail with respect to its function.

A feature of the present invention is that in a composite material composition using a polymer as a binder component, it is used instead of an organic synthetic polymer such as a thermosetting resin or a thermoplastic resin, which has been conventionally used as a polymer, and then used as a household shock absorber or a heat insulating material packaging material. It is to recycle the waste expanded polystyrene generated as.

Waste foamed polystyrene is composed of 98% air and 2% polystyrene, and when dissolved using a styrene monomer or methyl methacrylate as a reactive solvent as in the present invention, the air contained in the foamed polystyrene is stored in each cell ( The solution is excluded from the cell, and the solution is in a form in which the polymer is dispersed in the monomer, that is, a syrup phase. At this time, if the high molecular weight polystyrene is used in an excessively large amount, the viscosity of the solution becomes excessively high, so that the practical dissolution limit of the waste expanded polystyrene to the solvent is about 50%, and the styrene monomer or methyl to 1 to 50% by weight of the waste expanded polystyrene The amount of methacrylate to be used is about 45 to 94% by weight based on the weight of the total binder composition.

The polystyrene molecules in the waste foamed polystyrene solution are not directly involved in the polymerization reaction, but when copolymerized with styrene monomer or methyl methacrylate and the crosslinking trimethylropropane trimethacrylate, they form their own solids and are integrated with the polymerization product. It gives a high density of filling effect and binding force in the matrix, resulting in a strength enhancing effect of the cured product. Therefore, in consideration of workability, strength and the like, it is preferable that the optimum mixing amount of the waste expanded polystyrene is 25 to 30% by weight.

The dissolution tank used for dissolving waste foamed polystyrene is to be treated with flammable oil (second petroleum), so it must be used with explosion-proof structure or explosion proof structure. It is better to use the one with the device.

Thereafter, trimethyllopropane trimethacrylate is added to the waste foamed polystyrene solution prepared by dissolving waste foamed polystyrene in a styrene monomer or methyl methacrylate. Trimethyllopropane trimethacrylate is a highly reactive trifunctional monomer that plays a role of giving rigidity to the matrix by forming a polymer of three-dimensional network structure through copolymerization with styrene monomer or methyl methacrylate. When the amount of the crosslinking agent trimethyllopropane trimethacrylate is increased, not only the curing time is shortened but also the heat resistance, strength, and rigidity are increased. However, when the amount of the crosslinking agent is 50% by weight or more, the brittle fracture occurs. Since it will adversely affect the storage stability of the present invention, it is preferable to limit the amount of the mixture to 4 to 50% by weight.

Since the curing of the binder using the waste foamed polystyrene solution prepared above is performed by the action of a polymerization initiator and a polymerization accelerator, in a subsequent step, N, N-dimethyl-p-toluidine or an organic peroxide is used as a polymerization initiator in the binder composition. A polymerization promoter such as N, N-dimethylaniline is added.

The polymerization promoter serves to assist in the generation of active radicals that decompose the polymerization initiator to induce chain polymerization of the styrene monomer or the methyl methacrylate and copolymerize the styrene monomer or the methyl methacrylate with the crosslinking agent. Therefore, in the case of heating curing, since active radicals are generated by the thermal decomposition of the polymerization initiator to cause a polymerization initiation reaction, the addition of a separate polymerization promoter is unnecessary.

In the present invention, as the polymerization initiator, 0.5 to 3 Phr is added as an organic peroxide, for example, benzoyl peroxide, lauroyl peroxide, and bisperoxide, in parts by weight based on 100 parts by weight of the total amount of the binder, and as a polymerization accelerator. N, N-dimethyl-p-toluidine or N, N-dimethylaniline is added at 0.01 to 2 Phr for room temperature curing.

The curing time of the polymer composite material composition can be adjusted by adjusting the addition amount of the polymerization initiator and the polymerization promoter.In consideration of the strength and economic efficiency of the cured product, each addition amount is 2 Phr for the total resin amount, and the polymerization is performed. The promoter is preferably 0.5 Phr.

The silane coupling agent, which is another component of the present invention, serves to enhance the interfacial adhesion between the organic material, the binder, and the inorganic material, and the filler. The strength of the silane coupling agent is increased by about 10 to 30% by the addition of the silane coupling agent. The effect is shown. In the present invention, γ-methacryloxypropyltrimethoxy silane is used as the silane coupling agent in the range of 0.01 to 1.5 Phr, and preferably about 1 Phr is used.

After adding and mixing the above-described binder main ingredient and other auxiliary ingredients, an appropriate amount of aggregate and filler is added and mixed according to a conventional polymer concrete and mortar manufacturing method, followed by beam forming, and molding into a predetermined shape and size using a mold mold. Then, the cured composite material is prepared by curing at room temperature of about 20 ° C. for 5 hours to 7 days and / or by heating curing at a temperature of about 65 to 80 ° C. for 5 hours to 24 hours.

At this time, the aggregate is selected from the group consisting of sand, crushed stone, subsidiary sand, silica sand, waste foundry sand, fine aggregate, wood wool, wood chips, wood chips and waste tire powder, and as a filler, calcium carbonate, silica, fly ash, cement or gypsum. Etc. The content of these aggregates and fillers in the composite material should be selected in consideration of their type and particle size, the method of curing the polymer composite material produced using them, and the properties and uses required for the desired cured product. The blending ratio is usually suitably used in the range of 10 to 20% by weight of the binder, 60 to 80% by weight of the aggregate, and 10 to 20% by weight of the filler based on the weight of the total polymer composite material.

Hereinafter, the present invention will be described in detail with reference to the manufacturing process of the binder composition and the polymer composite material of the present invention and physical property tests thereof.

The following examples are provided to illustrate and explain the present invention in more detail, and the scope of the present invention should not be understood as being limited only to the following examples.

EXAMPLE

In the present embodiment, according to the present invention, a binder composition mainly composed of waste foamed polystyrene solution and a polymer composite material including the same are prepared, and various physical performance tests such as working life, bending strength, and compressive strength thereof are performed. It is intended to demonstrate the superiority of the polymer composite material of the present invention by comparing the results with conventional polymer composite material compositions.

In this example, a total of three polymer mortars using the binder of the present invention and the conventional binder composition were prepared and tested as polymer composite materials, respectively.

Specifically, as shown in Table 1 below, 28 wt% of waste foamed polystyrene, 47 wt% of styrene monomer, and 25 wt% of trimethyllopropane trimethacrylate were used as main components, and 1.0 Phr (binder as a secondary component) was used. By weight of the main component combined parts by weight), 2.0 Phr of benzoyl peroxide and 0.5 Phr of N, N-dimethyl-p-toluidine, together with the present polymer binder for comparison, presently polymer concrete and mortar Two conventional polymer binders each having an unsaturated polyester resin and a polymethyl methacrylate resin, which are widely used as binders for composite materials, were used.

The polymer binder of the present invention was prepared by dissolving waste expanded polystyrene having a density of about 15 kg / m 3 in an industrial styrene monomer, cooling to room temperature, mixing trimethylpropane trimethacrylate, and then adding various auxiliary components.

The components and contents of each of the polymer binder, conventional unsaturated polyester binder and polymethyl methacrylate binder of the present invention are shown in Table 1 below, and the conventional polymer binder used for comparison is most commonly used. It was prepared by selecting a composition ratio that is considered to be.

Composition ratio of binder for polymer mortar Ingredient Name content Binder of the Invention chief ingredient Waste foamed polystyrene 28 wt% Styrene monomer 47 wt% Trimethyllopropane Trimethacrylate 25 wt% Supplementary Ingredients Silane coupling agent 1.0 Phr Benzoyl peroxide 2.0 Phr N, N-dimethyl-p-toluidine 0.5 Phr Polyester binder chief ingredient Unsaturated polyester resin 50 wt% Styrene monomer 50 wt% Supplementary Ingredients Methyl ethyl ketone peroxide 0.5 Phr Octanoic acid cobalt 0.5 Phr Polymethyl Methacrylate Binder chief ingredient Methyl methacrylate 67.4 wt% Trimethyllopropane Trimethacrylate 1.8 wt% Unsaturated polyester resin 23.1 wt% Polyisobutyl methacrylate 7.7 wt% Supplementary Ingredients Benzoyl peroxide 2.0 Phr N, N-dimethyl-p-toluidine 0.5 Phr

Using the binder, the polyester binder and the polymethyl methacrylate binder of the present invention prepared in the components and contents shown in Table 1 as binder components, respectively, silica sand (No. 4 and No. 7) as aggregate and calcium carbonate as filler Was prepared in the amounts shown in Table 2 to prepare three types of polymer mortars of the present invention polymer mortar (Example 1), polyester mortar (Comparative Example 1) and polymethyl methacrylate mortar (Comparative Example 2) .

Mixing ratio of polymer mortar Ingredient Name Binder Filling Material (Calcium Carbonate) Aggregate No. 4 No. 7 Content (% by weight) 18.0 16.4 49.2 16.4

The three polymer mortars prepared at the compounding ratios shown in Table 2 above were molded using a mold of 40 mm × 40 mm × 160 mm, and then cured by curing at room temperature for 7 days at 20 ° C. and 20 After curing at room temperature for 1 day at room temperature and cured by heating and curing at 70 ℃ for 15 hours to obtain a cured product, two kinds of cured cured product.

Tests for usable time, flexural strength and compressive strength for each resulted in test values as shown in Table 3 below.

Physical Performance for Examples and Comparative Examples Available time (minutes) Flexural strength (MPa) Compressive strength (MPa) Room temperature curing Room temperature curing + heating curing Room temperature curing Room temperature curing + heating curing Example 1 (Polymer Mortar of the Invention) 30 19.1 23.3 65.3 102.4 Comparative Example 1 (Polyester Mortar) 36 20.0 30.0 55.1 93.0 Comparative Example 2 (Polymethyl methacrylate mortar) 30 24.0 31.2 73.0 107.3

According to Table 3, in the case of the polymer mortar (Example 1) of the present invention using the waste foamed polystyrene solution as a binder, the conventional polyester mortar (Comparative Example 1) and polymethyl methacrylate mortar (Comparative Example 2) Compared to the available time, the flexural strength and the compressive strength are also inferior at all, especially in terms of compressive strength, both room temperature curing and room temperature curing + heating curing compared to the polyester mortar (Comparative Example 1) is rather high values appear.

Since the binder composition of the present invention and the polymer composite material including the same use waste foamed polystyrene generated in a large amount as waste, a conventional polymer composite using unsaturated polyester resin, epoxy resin, polymethyl methacrylate resin, etc. as a binder component. The manufacturing cost is lower than that of the material, and the physical performance such as bending strength and compressive strength is also advantageous in that it has a performance corresponding to that of the existing composite material.

In addition, since the present invention uses a solution in which waste foamed polystyrene is dissolved in a reactive solvent, styrene monomer or methyl methacrylate, as a binder for a polymer composite material, a separate solvent separation process is not required. It requires no equipment and can be manufactured with simple dissolving and mixing equipment, which saves costs and shortens the process compared to other recycling methods.

Therefore, the present invention is a groundbreaking way to recycle the waste expanded polystyrene for construction materials, has excellent effect of replacing the synthetic polymer, and less energy consumption or secondary pollution compared with the conventional waste foamed polystyrene recycling method, the global environment It also has an excellent effect in terms of environmental protection with low load on.

Claims (11)

1 to 50% by weight of waste expanded polystyrene (EPS), 45 to 94% by weight of styrene monomer (SM) or methyl methacrylate (MMA) as a reactive solvent and 4 to 50% by weight of trimethyl as crosslinking agent relative to the total composition A binder composition for a polymer composite material, comprising propane trimethacrylate (TMPTMA). The method of claim 1, 0.01 to 1.5 Phr (Parts per hundred parts of resin) as a coupling agent (in parts by weight based on the combined amount of waste foamed polystyrene, styrene monomer or methyl methacrylate and trimethylropropane trimethacrylate) A binder composition for a polymer composite material, further comprising 0.5 to 3 Phr of organic peroxide as a silane and a polymerization initiator. The method of claim 2, The said silane is (gamma)-methacryloxypropyl trimethoxy silane, and the said organic peroxide is benzoyl peroxide, lauroyl peroxide, or bisperoxide, The binder composition for polymeric composite materials characterized by the above-mentioned. The method of claim 2, When the polymer composite material is cured at room temperature, the polymer further comprises 0.01 to 2 Phr of N, N-dimethyl-p-toluidine (DMT) or N, N-dimethylaniline (DMA) as a polymerization accelerator. Binder composition for composite materials. In a polymer composite material comprising an aggregate, a filler and a binder composition, the binder composition comprises 1 to 50% by weight of waste expanded polystyrene, 45 to 94% by weight of styrene monomer or methyl methacrylate as a reactive solvent, based on the total binder composition weight. A polymer composite material comprising 4 to 50% by weight of trimethyllopropane trimethacrylate as a rate and a crosslinking agent. The method of claim 5, And wherein the binder composition further comprises 0.01 to 1.5 Phr of silane as coupling agent and 0.5 to 3 Phr of organic peroxide as polymerization initiator. The method of claim 6, The said silane is (gamma) -methacryloxypropyl trimethoxy silane, and the said organic peroxide is benzoyl peroxide, lauroyl peroxide, or bis peroxide, The polymer composite material characterized by the above-mentioned. The method of claim 6, When curing the polymer composite material at room temperature, the binder composition further comprises 0.01 to 2 Phr of N, N-dimethyl-p-toluidine or N, N-dimethylaniline as a polymerization accelerator. . The method of claim 5, Wherein said polymeric composite material is polymeric concrete or polymeric mortar. The method of claim 5, The aggregate is sand, crushed stone, broken sand, silica sand, waste foundry sand, fine aggregate, wood wool, wood chips, wood chips or waste tire powder, and the filler is calcium carbonate, silica, fly ash, cement or gypsum. . A method for producing a cured polymer composite material, wherein the polymer composite material of claim 5 is mixed, vibrated and molded, followed by room temperature and heat curing.