KR102475551B1 - Composite composition comprising livestock excretions, composite using the same and method for preparing the same - Google Patents

Abstract

The present invention relates to a composite material comprising livestock manure compost and a method for manufacturing the same, and more particularly to livestock manure compost; thermoplastic resin; and an additive composition comprising a hydrophobic acrylic monomer, cardanol, and a crosslinking agent; Composites manufactured using this; and a method for producing a composite material comprising the steps of providing the composition for preparing a composite material, forming the composition by heating and extruding the composite material, and irradiating the molded extrudate with an electron beam.

Description

Composition for preparing a composite material containing livestock manure compost, a composite material using the same, and a method for manufacturing the same

The present invention relates to a composition for preparing a composite material including livestock manure compost, a composite material using the same, and a method for manufacturing the same, and relates to a composite material including livestock manure compost with improved physical properties such as thermal stability and tensile strength, and a method for manufacturing the same.

Recently, the number of livestock raised due to dense breeding of livestock is increasing worldwide, and due to such an increase in numbers, a large amount of livestock manure is generated, resulting in various problems including pollution. On the other hand, livestock manure contains a lot of fertilizer components such as various organic compounds and nitrogen phosphate, so it is used as manure for crops or fruit trees by manufacturing compost using it. and the application of livestock manure compost.

On the other hand, among wood composites, WPC (Wood-Plastic-Combination, Wood-Polymer-Composite, etc.) is obtained by impregnating wood with a liquid curable resin or polymerizable monomer and then curing it. It can be improved and is widely used in building materials. Wood flour plastic, an eco-friendly low-carbon new material, combines wood flour, which is a natural material, and olefin-based thermoplastic polymer resin, which is harmless to the human body, through special kneading and processing, and extrusion and injection molding are easy. It is an eco-friendly material that can be recycled 100% and has advantages such as luxurious natural texture of wood, durability of polymer resin, water resistance, and molding processability.

However, limitations include carbonization of wood powder with low thermal stability during extrusion and injection molding processing, mechanical properties due to weakening of the interfacial adhesion between plastic and wood powder during the cooling process of molded products, and reduced preservative properties due to increased moisture content of wood powder due to hydrophilicity. there is In order to overcome this problem, chemical additives such as highly toxic flame retardants, preservatives, and flame retardants are used, resulting in problems such as environmental hormones.

For example, Korean Patent Publication No. 10-2008-0103734 discloses a biocomposite material with improved mechanical strength containing a biodegradable polymer, a main material made of a cellulose-based natural material, and a hydrolysis inhibitor, but diisopropyl -It is a technique that requires the inclusion of a hydrolysis inhibitor such as phenyl isocyanate. In addition, in general, when strength is secured, ductility is insufficient, but there is a demand for applications requiring not only strength but also excellent ductility.

Therefore, when a composite material with improved thermal stability and mechanical properties is developed without requiring such harmful compounds by using livestock manure compost, it is expected that it can be applied in a variety of related fields.

One aspect of the present invention is to provide a composition for preparing a composite material from which a composite material having improved mechanical properties and thermal stability can be obtained.

Another aspect of the present invention is to provide a composite with improved mechanical properties and thermal stability.

Another aspect of the present invention is to provide a method for manufacturing the composite material of the present invention described above.

According to one aspect of the present invention, livestock manure compost; thermoplastic resin; and an additive composition comprising a hydrophobic acrylic monomer, cardanol, and a crosslinking agent.

According to another aspect of the present invention, a composite material prepared using the composition for preparing a composite material of the present invention is provided.

According to another aspect of the present invention, providing a composition for preparing a composite material of the present invention; Molding by heat-extruding the composition for preparing a composite material; And there is provided a method for producing a composite material comprising the step of irradiating an electron beam to the molded extrudate.

According to the present invention, a composite material with improved mechanical properties and thermal stability can be provided by manufacturing a composite material including livestock manure compost using radiation technology.

1 shows the results of morphological analysis (a) and average particle size analysis (b) for each particle size of livestock manure compost separated using a particle separator (sieve).
2 shows a graph (a) and a component analysis table (b) of elemental analysis results for each particle size of livestock manure compost analyzed using EDX.
3 is a graph showing the results of pyrolysis analysis by particle size of livestock manure compost analyzed using TGA.
Figure 4 (a) shows the viscosity measurement result according to the content ratio of the additive composition using a viscometer, Figure 4 (b) is the result of confirming the degree of crosslinking through the measurement of the gel fraction (%) according to the electron beam irradiation dose is shown.
Figure 5 shows the results of tensile strength analysis of composite materials obtained on the basis of each composition of Comparative Examples and Examples.
Figure 6 shows the results of analysis of the flexural strength of composites obtained on the basis of each composition of Comparative Examples and Examples.

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, the embodiments of the present invention may be modified in various forms, and the scope of the present invention is not limited to the embodiments described below.

According to one aspect of the present invention, a composition for preparing a composite material containing livestock manure compost, and a composite material using the same are provided. The composite of the present invention can solve the problem of mechanical strength reduction due to carbonization of wood during thermoforming processing of plastic composites (WPC, Wood-Plastic-Combination, Wood-Polymer-Composite) using wood, and furthermore, has excellent physical properties have

More specifically, the composition for preparing a composite material of the present invention for manufacturing such a composite material is livestock manure compost; thermoplastic resin; and an additive composition including a hydrophobic acrylic monomer, cardanol, and a crosslinking agent.

Livestock manure compost that can be used in the present invention is a material with a fertilizer component made by fermenting livestock manure, and is not particularly limited as long as it contains major nutrients such as nitrogen, phosphoric acid, and potassium and various micronutrients. It is decomposed by aerobic microorganisms under the condition that air is supplied, and as a result, it is converted into major nutrients such as nitrogen, phosphoric acid, and potassium, which are fertilizer components, and various micronutrients.

The livestock manure compost may be purchased commercially or prepared using livestock manure.

For example, when manufacturing livestock manure compost, observe the appropriate moisture content (about 75%) when composting, supply air in the compost heap (150 liters per 1 cubic meter per 1 m3), and in the case of dairy cow and Korean cattle farms. Since most of them use composting sand, it is desirable to produce good quality compost by crushing the aggregated manure into small pieces and turning the compost heap over to facilitate air supply when composting the collected livestock manure. On the other hand, since pig manure has a high water content, a water separation process can be performed before composting, and a water regulator can be used. Chicken manure with a low digestibility has high nutrients in the manure, so it easily decays when accumulated in the barn, so it is composted immediately after discharge. For example, you can refer to materials such as the introduction of livestock manure composting technology provided by the Rural Development Administration.

Meanwhile, the livestock manure compost used in the present invention is preferably a powder having a particle size of 100 μm or less, and for example, it may be a powder having a particle size of 90 μm or less. When the livestock manure compost has a particle diameter of 100 μm or less, as can be seen in FIGS. 2 and 3, the content of inorganic substances such as Si in the livestock manure compost powder is relatively increased, and thus thermal stability can be increased. In this case, the livestock manure compost may be a powder having an average particle diameter of 80 to 140 μm, for example, a powder having an average particle diameter of 90 to 130 μm.

A method of obtaining livestock manure compost in the above range is not particularly limited, and for example, a sieve or the like may be used.

The thermoplastic resin that can be used in the present invention may be at least one selected from the group consisting of polyethylene, polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, polystyrene, and polypropylene, preferably polyethylene.

Meanwhile, the hydrophobic acrylic monomer used in the present invention may be a monofunctional to trifunctional acrylic monomer, preferably a monofunctional acrylic monomer.

For example, the monofunctional acrylic monomer may be at least one selected from the group consisting of 3-(Trimethoxysilyl)propyl methacrylate (TMPMA), 2-(Dimethylamino)ethyl methacrylate (DMEMA), and dipentaerythritol hexaacrylate (DPEHA). However, it is not limited thereto, and is preferably TMPMA (3-(Trimethoxysilyl)propyl methacrylate).

The difunctional acrylic monomer is 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol, 1,3-butanediol dimethacrylate, bis(4-methacryloylthiophenyl) ) Sulfide, 1,9-bis (acryloyloxy) nonane, 1,4-bis (acryloyloxy) butane, 1,6-bis (acryloyloxy) hexane, 1,10-bis (acryloyloxy)decane, glycerol dimethacrylate, 1,6-bis(acryloyloxy)-2,2,3,3,4,4,5,5-octafluorohexane, di Group consisting of ethylene glycol dimethacrylate, dipropylene glycol diacrylate, 1,12-dodecanediol dimethacrylate, diethylene glycol diacrylate, ditrimethylolpropane tetraacrylate and ethylene glycol dimethacrylate It may be one or more selected from.

On the other hand, the trifunctional acrylic monomer is 1,6-hexanediol dimethacrylate, 4,4'-isopropylidenediphenol dimethacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacryl Rate, nonamethylene glycol dimethacrylate, pentaerythritol tetraacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacryl from the group consisting of tetraethylene glycol diacrylate, tris(2-acryloyloxyethyl) isocyanurate, tripropylene glycol diacrylate, tetraethylene glycol dimethacrylate and tetramethylene glycol dimethacrylate There may be one or more selected.

Meanwhile, the crosslinking agent that can be used in the present invention is triallyl isocyanurate (TAIC), trimethylolpropane triacrylate (TMPTA), hexandiol diacrylate (HDDA), tri It may be at least one selected from the group consisting of triallyl cynurate (TAC) and tripropylene glycol diacrylate (TPGDA), preferably triallyl isocynurate. .

The additive composition used in the present invention includes a hydrophobic acrylic monomer, cardanol, and a crosslinking agent, and the additive composition contains 45 to 80% by weight of a hydrophobic acrylic monomer and 1 to 15% by weight of cardanol, based on the total weight of the additive composition. and 10 to 45% by weight of a crosslinking agent, for example, 50 to 80% by weight of a hydrophobic acrylic monomer, 5 to 15% by weight of cardanol, and 10 to 40% by weight of a crosslinking agent.

If the amount of the hydrophobic acrylic monomer in the additive composition is less than 45% by weight, crosslinking may be insufficient and the tensile strength of the composite material may be lowered when irradiated with electron beams for preparing a composite material, and if it exceeds 80% by weight, thermal melting due to high-density crosslinking may occur. There is a problem that cannot be recycled because it is not done.

In the additive composition, if the cardanol is less than 1% by weight, it is insufficient in terms of hydrophobic surface treatment and there is a problem in improving physical properties. can

On the other hand, if the crosslinking agent in the additive composition is less than 10% by weight, crosslinking may be insufficient during manufacture of the composite material, and if it exceeds 45% by weight, physical properties of the composite material such as tensile strength may be rather deteriorated.

Meanwhile, the composition for preparing the composite material of the present invention preferably includes 10 to 45% by weight of livestock manure compost, 50 to 80% by weight of a thermoplastic resin, and 0.1 to 10% by weight of an additive composition, for example, 30 to 45% by weight of livestock manure compost. % by weight, 50 to 70% by weight of the thermoplastic resin and 0.5 to 5% by weight of the additive composition.

In the composition for preparing the composite material of the present invention, when the livestock manure compost is less than 10% by weight based on the weight of the composition for preparing the composite material, there is a problem in that the increase in thermal stability of the composite material is insufficient, and when it exceeds 45% by weight, it is mixed with a polymer There is a problem of deterioration of physical properties.

In addition, when the thermoplastic resin is less than 50% by weight based on the weight of the composition for preparing a composite material, there is a problem of insufficient mechanical properties, and when it exceeds 80% by weight, there is a problem of poor thermal stability or relatively low livestock manure compost. There is a problem that the increase in thermal stability of the composite is insufficient due to the decrease in the content.

On the other hand, if the additive composition is less than 0.1% by weight based on the weight of the composition for preparing a composite material, there is a problem of insufficient crosslinking during electron beam irradiation, and if it exceeds 10% by weight, problems in remelting the polymer due to increased crosslinking degree there is

Furthermore, according to the present invention, a composite material prepared using the above-described composition for preparing a composite material of the present invention is provided, and the composite material of the present invention has improved mechanical properties and thermal stability.

In more detail, the composite material of the present invention comprises the steps of providing the composition for preparing the composite material of the present invention described above; Molding by heat-extruding the composition for preparing a composite material; And it can be produced by a method for producing a composite material comprising the step of irradiating the molded extrudate with an electron beam.

The molding step is preferably performed at a temperature range of 170 to 250 °C, and more preferably, for example, performed at a temperature range of 190 to 230 °C. If the temperature in the molding step is less than the above range of 170 ° C, molding may not be performed smoothly, and if it exceeds the above 250 ° C range, mechanical properties of the composite material may deteriorate due to thermal decomposition of the thermoplastic resin. have.

Meanwhile, the cutting step after molding may be performed after cooling, for example, cutting may be performed after cooling to a temperature of 40 to 80° C.

The step of irradiating the electron beam may be performed at a dose of 1 kGy to 50 kGy, preferably the step of irradiating the electron beam is performed at a dose of 10 kGy to 40 kGy, for example, a dose of 10 kGy to 30 kGy. is performed with If the dose is less than the above range, the physical properties of the composite material may be insufficiently improved due to insufficient crosslinking of the composite material, and if the dose exceeds the above range, the composite material may be decomposed and the physical properties of the composite material may be reduced.

Furthermore, the step of irradiating the electron beam is preferably performed with an electron beam energy of 5 to 15 MeV, for example, 5 to 13 MeV, more preferably 5 to 10 MeV. If it is less than the above range, physical properties of the composite material may be insufficiently improved, and if it exceeds the above range, the composite material may be decomposed and physical properties such as flexural strength may be rather reduced.

As described above, according to the present invention, by manufacturing a composite material containing livestock manure compost using radiation technology, a composite material with improved mechanical properties and thermal stability can be provided, thereby solving the problems of conventional biomass-based composite materials. have.

Hereinafter, the present invention will be described in more detail through specific examples. The following examples are merely examples to aid understanding of the present invention, and the scope of the present invention is not limited thereto.

Example

1. Preparation of Composition for Manufacturing Composites Containing Livestock Manure Compost

(1) Preparation and characterization of livestock manure compost

The livestock manure obtained (purchased) from the Dangjin World Agricultural Cooperative was classified into particle size groups of 150 μm or less (group 1), 100 μm or less (group 2), and 90 μm or less (group 2) using a particle separator (sieve). separated.

The result of confirming the powder of each group at 50 magnification using a scanning electron microscope is shown in FIG. 1 (a), and the average particle size of each group is analyzed and shown as a graph in FIG. 1 (b).

On the other hand, element analysis was performed for each particle size of livestock manure compost using EDS (Energy Dispersive X-ray spectrometer, Ultim Max), and the result graph (a) and component analysis table (b) are shown in FIG. 2.

3 is a graph showing the results of pyrolysis analysis by particle size of livestock manure compost analyzed using TGA (Thermogravimetric analysis, Mettler-Toledo), and for comparison, wood flour (Gbiotech, wood flour) with a particle diameter of 100 μm was analyzed together.

In this experiment, different characteristics for each particle size of livestock manure compost were confirmed, and in the case of livestock manure compost with a particle size of 100 μm or less, in particular, livestock manure compost with a particle diameter of 90 μm or less, the content of inorganic components such as Si increases, Therefore, it was confirmed that the passion stability was increased.

(2) Composition for preparing a composite material containing livestock manure compost

1) Preparation of additive composition and confirmation of its physical properties

Triallyl cyanurate (TAIC), dipentaerythriol hexaacrylate (DPEHA) and cardanol (Cardanol, Keumgang Green Co., Ltd.) 80:10:10 (Preparation Example 1), 45:45: Additive compositions were prepared by mixing at weight ratios of 10 (Preparation Example 2), 45:50:10 (Preparation Example 3) and 10:80:10 (Preparation Example 4).

The viscosity of the additive composition of each preparation example was measured at 300 to 600 rmp using a viscometer through a mixing process, and the results are shown in FIG. 4 (a).

On the other hand, Figure 4 (b) was measured by Soxhlet extraction method to measure the crosslinking rate of the polymer composite material crosslinked using an electron beam in each additive composition of Preparation Examples 1, 2 and 4. After measuring the weight of each sample (0.5 cm × 0.5 cm, n = 5), it was supported in xylene and heated at 140 ° C. for 8 hours to remove unreacted substances. After drying for 12 hours using a vacuum oven, the weight of the sample obtained through natural drying for 4 hours was measured. The crosslinking rate was measured using each weight.

2) Preparation of Composition for Manufacturing Composites

After mixing polyethylene and two groups of livestock manure compost having a particle diameter of 100 μm or less in a weight ratio of 60:40 to obtain a mixture, 1 part by weight of the additive composition per 100 parts by weight of the mixture was mixed to obtain a composition for preparing a composite material. manufactured. At this time, the additive composition was obtained by using the additive compositions obtained in Preparation Examples 1 to 4, respectively, Comparative Example 1 for the case of using the additive composition of Preparation Example 1, Example 1 for the case of using the additive composition of Preparation Example 2, and Preparation The case of using the additive composition of Example 3 is referred to as Example 2, and the case of using the additive composition of Preparation Example 4 is referred to as the composition for preparing a composite material of Example 3, respectively.

2. Manufacture of Composites Containing Livestock Manure Compost

An example in which the composition for preparing a composite material of Comparative Example 1 and Examples 1 to 3 obtained in 1.2) and the livestock manure compost used in the composition for preparing a composite material of Example 2 were replaced with one group having a particle diameter of 150 μm or less. A composition for preparing a composite material of Example 5, which was replaced with 3 groups of livestock manure compost having a particle diameter of 4 and 90 μm or less, was prepared.

The composition for preparing each of the composites was mixed with polyethylene, livestock manure compost and additive composition at 180 ° C., screw speed 170, torque while maintaining the temperature of the blender (Brabender, Lab-station) at 180 to 230 ° C. 43, After blending for 20 minutes, use a hot press to melt the sample sufficiently for about 10 minutes, then increase the pressure to 30 MPa over 5 minutes, and after 5 minutes, mold cooling press (mold) at room temperature A sheet was prepared by cooling under a pressure of 7 MPa using a cooling press).

For each composite material, an electron beam of 10 to 30 kGy was irradiated using an electron beam accelerator (10 MeV) to obtain a crosslinked composite material irradiated with electron beam.

3. Confirmation of physical properties of cross-linked composites containing livestock manure compost

(1) Tensile strength

To confirm the mechanical properties of the cross-linked composite, they were measured using a universal testing machine (UTM, Instron 5982, Norfolk, MA, USA). The sample was manufactured according to the ASTM D638 standard, and was measured under the conditions of a load range of 100 kN and 50 mm/min.

As can be seen in FIG. 5 , it was confirmed that the tensile strength increased in the case of composites based on the compositions of Examples 1 to 3 of the present invention.

(2) Flexural strength

Using the composite material compositions obtained in each of the Preparation Examples and Comparative Examples, a cross-linked composite material was prepared as a sheet sample of 45 mm x 45 mm x 2.4 mm, and 2 mm in a direction perpendicular to the specimen according to the flexural strength test procedure of ASTM D790. The force (load) was applied at a rate of /min to record the force at the breaking point, and the results are shown in the graph of FIG. 6 .

Referring to the results of FIG. 6 , it was confirmed that improvement in flexural strength was obtained in the composites in which the composite compositions of Examples 1 to 5 of the present invention were crosslinked.

Although the embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and variations are possible without departing from the technical spirit of the present invention described in the claims. It will be obvious to those skilled in the art.

Claims (13)

livestock manure compost powder having an average particle diameter of 80 to 100 μm;
thermoplastic resin; and
An additive composition comprising 45 to 80% by weight of a hydrophobic acrylic monomer, 1 to 15% by weight of cardanol, and 10 to 45% by weight of a crosslinking agent,
10 to 45% by weight of livestock manure compost, 50 to 80% by weight of a thermoplastic resin, and 0.1 to 10% by weight of an additive composition based on the weight of the composition for preparing a composite material,
The hydrophobic acrylic monomer is at least one acrylic monomer selected from the group consisting of TMPMA (3-(Trimethoxysilyl)propyl methacrylate), DMEMA (2-(Dimethylamino)ethyl methacrylate) and DPEHA (dipentaerythritol hexaacrylate),
The crosslinking agent is triallyl isocyanurate (TAIC), trimethylolpropane triacrylate (TMPTA), hexandiol diacrylate (HDDA), triallyl cyanurate (triallyl cynurate, TAC), and at least one selected from the group consisting of tripropylene glycol diacrylate (TPGDA), a composition for preparing a composite material.
The composition for preparing a composite material according to claim 1, wherein the livestock manure compost is a powder having a particle size of 100 μm or less.
delete delete delete According to claim 1, wherein the thermoplastic resin is at least one selected from the group consisting of polyethylene, polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, polystyrene, and polypropylene, the composition for preparing a composite material.
delete delete A composite material manufactured using the composition for preparing a composite material according to any one of claims 1, 2 and 6.
Providing a composition for preparing a composite material according to any one of claims 1, 2 and 6;
Molding by heat-extruding the composition for preparing a composite material; and
Step of irradiating the molded extrudate with an electron beam
Method for producing a composite material comprising a.
11. The method of claim 10, wherein the forming step is performed at a temperature range of 170 to 250 °C.
11. The method of claim 10, wherein the step of irradiating the electron beam is performed at a dose of 1 kGy to 50 kGy.
11. The method of claim 10, wherein the step of irradiating the electron beam is performed with an electron beam energy of 5 to 15 MeV.

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