KR101298525B1 - Hybrid Binder Composition Based on Depolymerizate of Polyurethane and Method of Using the Same - Google Patents

Abstract

The present invention provides a method for recycling depolymerized polyurethane scrap. The present invention provides a hybrid binder composition comprising depolymerized polyurethane scrap and pretreated soybean oil and polypropylene glycol. In the present invention, it is preferable that the above-mentioned hybrid binder composition is mixed with the rubber chip for elastic packaging, cured with a curing agent, and used as a binder for the elastic packaging material. These hybrid binder resins contribute to resource saving and circulation by recycling polyurethane scrap, and can be stored at a relatively low temperature to save energy, and have no toxic problem for workers, while maintaining the binder's performance at an equivalent level. It shows economic advantages.

Description

Hybrid Binder Composition Using Polyurethane Depolymerization and Method of Using the Binder Composition Based on Depolymerizate of Polyurethane and Method of Using the Same

The present invention relates to a hybrid binder composition using a polyurethane depolymerizing method and a method of using the same, and more particularly, to obtain a depolymerization using a glycol or an amine as a polyurethane scrap, and to the depolymerization by adding an auxiliary raw material harmless to the human body. The present invention relates to a hybrid binder composition obtained by chemical treatment, a method for producing the same, and a method of curing the hybrid binder composition with a predetermined curing agent and using the same as a binder.

Today, binders are being used to combine compositions of various composite materials and to act as a medium. The adhesive used for bookbinding is also used as a kind of binder. Recently, with increasing interest in health and well-being, elastic material packaging has been made in various walkways and playgrounds. The construction of the elastic material packaging is performed by hardening a rubber chip as a main material and mixing a polyurethane binder as a binder therein.

Polyurethane resin is capable of realizing a variety of physical properties from soft to hard according to the selection of the raw material and has a good adhesion. However, in general, polyurethane raw materials can be said to be a disadvantage that the price is relatively expensive. In addition, when constructing the elastic material packaging using the polyurethane binder, since the isocyanate compound in the polyurethane raw material is harmful to the human body, care must be taken not to cause vapor toxicity due to isocyanate to the worker in the heating compaction process using a roller.

On the other hand, polyurethane scrap generated after the use of polyurethane is generated in large quantities in the recycling center of industrial sites and home appliances. Such polyurethane scrap has been pointed out as an environmental pollutant as industrial waste, but it is very preferable from an environmentally friendly point when recycling it.

Conventionally, technologies for recycling polyurethane foam scraps can be classified into physical recycling methods that are physically crushed and used again to manufacture polyurethane foams, and chemical recycling methods that are utilized through chemical treatment processes.

In the case of the physical recycling method, when the polyurethane foam scrap contains a large amount of foreign matter, the quality of the recycled product deteriorates due to the foreign matter. Therefore, the physical recycling method has various difficult characteristics in practice such as requiring a separate process to remove the foreign matter. have. This method is already being used in industrial sites, but it is a reality that it is difficult to remove foreign substances.

On the other hand, in the chemical recycling method, a low molecular weight glycol or amine is added to the polyurethane scrap and heated to a high temperature to decompose to obtain a depolymerized product, and to use the depolymerized product. However, the depolymerized product obtained here is a mixture of by-products generated during the depolymerization process, resulting in undesirable results in terms of product performance. In this respect, it can be said that the conventional chemical recycling method also has technical limitations.

In addition, the conventional polyurethane scrap was recycled in the form of foam again using polyurethane scrap as a main raw material, because the polyurethane was mainly utilized in the form of foam based on its rich physical properties.

Thus, until now, recycling of polyurethane scrap has been very limited in its application range or application method, and has a limitation that cannot be exceeded in a certain range.

The present invention is to improve the disadvantages of the prior art, in order to further expand the range of use of polyurethane scrap, the polyurethane depolymerization of the binder by adding a raw material harmless to the human body as a main raw material of polyurethane scrap The purpose is to switch to.

Another object of the present invention is to provide a method of using the above-mentioned depolymerized polyurethane scrap as a main raw material as a binder of an elastic material packaging rubber chip using a hybrid binder composition.

According to the present invention, when the above-described hybrid binder is used for elastic pavement such as a walkway and a children's playground, the present invention exhibits the same performance as that of the conventional polyurethane binder, and is considered to be a very environmentally friendly and economical solution.

In the present invention, in order to recycle the polyurethane scrap in the binder used for the elastic packaging, first, a depolymerization process using glycol or the like is required. The depolymerization process is a reaction for lowering the molecular weight of a polyurethane having a high molecular weight to break a urethane bond to generate a polyol and an amine. The depolymerized polyurethane scrap is possible to prepare a polyurethane again using polyisocyanate, but it is not easy to implement the physical properties necessary for use as a rubber chip binder for elastic packaging.

In the present invention, instead of producing a polyurethane-based binder using polyol and isocyanate, a hybrid type binder is produced using soybean oil and polyol in an environmentally friendly manner. This means converting the original polyurethane used in the form of a foam into the use of a binder in recycling by depolymerization. This means not to follow the initial use in terms of recycling of resources, but to convert the recycled product into secondary use at the time of recycling and to further expand its use. It means that there is.

The hybrid type binder composition according to the present invention can be usefully used as a binder of a packaging material using a rubber chip by inducing a curing reaction by using a chemical reaction of an amine group of a polyurethane depolymerized with a reactor of soybean oil and a hydroxyl group of a polyol.

Since the curing reaction of the amine group of the polyurethane depolymerization of the polyurethane and the reactor of soybean oil and the hydroxyl group of the polyol is possible at room temperature, the present invention does not require high temperature curing as in the prior art, and also does not use isocyanate which is harmful to worker's health. And at the same time has the advantage of implementing the same physical properties as the conventional polyurethane binder.

When manufacturing a hybrid type binder according to the present invention, it provides a basis for recycling the polyurethane scrap in a chemical method, there is an advantage to further improve the degree of recycling of the polyurethane scrap.

In addition, when manufacturing the hybrid type binder according to the present invention, it can be used for the rubber chip binder for elastic packaging to be installed in outdoor walkways, etc., there is an advantage that can be utilized as an economical binder manufacturing technology through resource recycling.

In addition, the present invention does not have a high-temperature isocyanate reaction process as in the prior art, and can perform a curing reaction at a low temperature, and above all, it is possible to prevent the possibility of inhalation of toxic substances by workers, and to save energy. There is an advantage.

In addition, the present invention also has the advantage that can be used by variously adjusting the physical properties of the final binder when the mixture of the functional group number and molecular weight of the polyol is appropriately selected.

1 is a typical scheme of the depolymerization reaction using a glycol of the polyurethane-based scrap used in the present invention,
2 is a chemical structural formula of pretreated soybean oil used in the present invention.

The present invention is a structural adhesive used as an organic binder, and includes a hybrid adhesive resin composition composed of an organic compound and a curing agent for curing it.

In the present invention, the above-mentioned hybrid adhesive resin composition contains a polyurethane scrap depolymerized product, pretreated soybean oil and a polyol as main components.

The hybrid adhesive resin composition according to the present invention contains a depolymerized product obtained by depolymerizing a polyurethane scrap.

The polyurethane scrap used in the present invention can be collected from various sources.

The polyurethane scrap is used in various industrial materials or can be obtained from industrial waste or waste of household appliances. Among them, in the case of a flexible polyurethane such as a car seat foam, for example, the crosslinking density of the network structure is formed through the reaction with the polyisocyanate using a polyol belonging to a relatively high molecular weight in the production of the polyurethane. Low and flexible characteristics. On the other hand, for example, when used in the manufacture of insulation foam of the refrigerator, since the molecular weight of the polyol and the number of functional groups is usually 4 or more on average, the crosslinking density of the net structure formed by the reaction with the polyisocyanate is high, and shows hard properties. Differences in the properties of various polyurethanes are also seen in chemical raw materials through depolymerization. For example, the depolymerization of rigid polyurethane foam is homogeneous, while depolymerization of soft polyurethane foam shows phase separation. This is because high molecular weight polyols and low molecular weight glycols and depolymerization products are limited in compatibility.

The present invention can be widely used without questioning the soft or hard properties of such polyurethane. In addition, the present invention can be utilized by depolymerizing various types of polyurethane scrap. When the polyurethane-based scrap is depolymerized, polyols, glycols and other amine compounds are produced, and the amine compounds are highly reactive and easily react with other organic compounds, especially the reactors of pre-treated soybean oil, at room temperature to cure. .

Figure 1 shows a typical reaction scheme of the depolymerization reaction using a glycol of the polyurethane-based scrap used in the present invention. When the depolymerization reaction of the polyurethane-based scrap is completed, it can be seen that a glycol containing a highly reactive amine and hydroxyl group is produced.

In the present invention, the depolymerization reaction of the polyurethane is usually carried out by cleaving the chain using the reactivity of the urethane group using glycol or amine at 180 ° C to 220 ° C. Small amounts of organometallic compounds may be added to accelerate the reaction rate. Depolymerization of polyurethane can be seen as exchange reaction with glycol. Examples of the glycol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and the like. And as an amine compound, diethanolamine, diethanol triamine, a triethanol tetraamine, etc. are mentioned. Polyurethane scrap and glycol or amine ratio of polyurethane scrap and glycol ratio of 1 ~ 1 ~ 2: 1 by weight is suitable.

The hybrid adhesive resin composition according to the present invention contains 100 to 500 parts by weight of pretreated soybean oil with respect to 100 parts by weight of the above depolymerized product.

The reason for using the soybean oil in the present invention can be exemplified as follows. First, the soybean oil is a vegetable raw material and does not contain harmful ingredients. This is not only harmless as a component of its own, but also means that when selecting a curing agent as a hybrid binder in the future, it is an important selection criterion in inducing harmlessness of the curing agent by avoiding the use of isocyanate which is harmful to the human body as in the prior art. do. Second, the soybean oil is a vegetable raw material can be easily purchased in Korea. This means ease of purchase and convenience in terms of resource economy. Third, since the soybean oil contains a large number of unsaturated fatty acids, it considers a very good reactivity.

The present invention is to select soybean oil in consideration of several factors as described above, the third reason of the above will be described in more detail as follows. The soybean oil has a vegetable unsaturated fatty acid obtained from soybean, and contains many unsaturated double bonds. Since unsaturated double bonds have a relatively unstable structure and easily react with each other, the more unsaturated double bonds in a reactant, the better.

In the present invention, it is preferable to use pretreated soybean oil in which the soybean oil is epoxidized using hydrogen peroxide or peroxide acid. In the present invention, the epoxidized soybean oil is referred to as 'pretreated soybean oil'. Since the pretreated soybean oil is an inexpensive natural material used as a plasticizer of polyvinyl chloride, it is also very advantageous to purchase and use it. When the pretreated soybean oil is used in an amount of 100 parts by weight or less, it is not preferable because the crosslinking density is too low, and when it is used in an amount of 600 parts by weight or more, it is not preferable.

Figure 2 is a structural formula showing the main components of pre-treated soybean oil that can be used in the present invention. The pretreated soybean oil used in the present invention is harmless to the human body and therefore does not have any detrimental effect on the workers. The pretreated soybean oil shows that there are at least six reactors that can be involved in the reaction.

The hybrid adhesive resin composition according to the present invention contains 10 to 200 parts by weight of polyol based on 100 parts by weight of the above depolymerized product. Since the polyol has a variety of functional groups and molecular weight products, it is preferable to select and use a suitable one for implementing binder properties. When the polyol is 10 parts by weight or less, it is not preferable because of lack of flexibility, and when it is 200 parts by weight or more, it is not preferable because of lack of rigidity.

In the present invention, the polyol refers to any one or two or more selected from the group consisting of ether-based polyols, ester-based polyols, caprolactone-based polyols, carbonate-based polyols, and polybutadiene polyols. The polyol is added to react with the polyurethane depolymerized to control its physical properties. In order to lower the crosslinking density and give ductility after curing of the hybrid binder, it is preferable to use polypropylene glycol and its analogs having a high molecular weight and a small number of functional groups.

This invention can harden | cure the said hybrid adhesive resin composition with a hardening | curing agent, and can use it as a structural adhesive agent of the rubber chip binder for elastic packaging.

In the present invention, the curing agent is one or two or more compounds selected from the group consisting of BF ₃ , AlCl ₃ , SnCl ₄ , TiCl ₄ used to be dispersed in polypropylene glycol. The curing agent induces a reaction with the hydroxyl group of the polypropylene glycol by opening the epoxy group corresponding to the reactor of the pre-treated soybean oil, thereby performing a function of converting the composition of the present invention into a network structure. In this case, the ring-opened epoxy group is also easily reacted with the amine compound already present in the binder composition.

In the present invention, the curing reaction is easy to occur even at a relatively low temperature, has the advantage that can be used as a binder at room temperature.

In order to prepare a hybrid binder composition having various physical properties in the present invention, the concentration of the pre-treated soybean oil and the hydroxyl group concentration of the polyol must be the same, or the concentration of the polyol hydroxyl group is lower than the concentration of the pre-treated soybean oil. Since the reactor of the pre-treated soybean oil can be copolymerized and homopolymerized, the hydroxyl group of the polyol can be copolymerized only, and if present in an excessive amount, it does not form a part of the crosslinked structure after curing and acts as a plasticizer and weakens physical properties.

Hereinafter, the present invention will be described in more detail.

One). Preparation of Polyurethane Depolymers

The semi-hard polyurethane foam scraps were pulverized to a diameter of 2 millimeters or less and introduced into diethylene glycol at 200 ° C. to prepare a depolymerized product. The ratio of polyurethane depolymer and diethylene glycol was 2: 1 by weight. In order to shorten the reaction time, 500 ppm of butoxy titanium was added as a catalyst for the depolymerization reaction, and a light brown liquid depolymerized product was obtained 4 hours after the start of the reaction. The hydroxyl equivalent value of the obtained depolymerized product was 110 g / eq.

2). Pretreated Soybean Oil

Pre-treated soybean oil obtained by treating soybean oil with peroxide water was purchased from commercially produced products. (Manufacturer: Sajo sea mark, a brand name: epoxy soybean oil). It was a colorless liquid product with an equivalent weight of 250 g / eq.

3). Polyol

Most preferably, polypropylene glycol is used as the polyol. This is because it contains a large number of hydroxyl groups, and can easily react with the amine group of the depolymerized product and the reactor of the pre-treated soybean oil. Since the pre-processed soybean oil includes a plurality of reactors, diol (PPG-400) and triol (PPG-2070) were purchased and used to prepare a binder of a flexible network structure. The products used were PPG-400 and PPG-2070 from Kumho Petroleum Co., Ltd. By changing the type and content of the polypropylene glycol according to the characteristics of the polyurethane depolymerization can implement the physical properties required for the final binder composition, but was limited to the above product once.

4). Curing Agent of Polyurethane Depolymerized Hybrid Binder

BF ₃ dietherate was selected and used as a curing agent for the reaction of polyurethane depolymerized with pretreated soybean oil and polypropylene glycol. This is in consideration of the reactivity and ease of use, the BF ₃ dietherate was used dispersed in polypropylene glycol. This is advantageous in terms of storage stability.

Hereinafter, specific embodiments of the present invention will be described.

Production Example 1

The polyurethane scrap was depolymerized in the usual manner as follows. 400 g of a hard polyurethane foam scrap used as a refrigerator insulation was divided into a four-necked flask reactor containing 200 g of monoethanolamine maintained at 160 and then subjected to depolymerization. In order to prevent loss of monoethanolamine, the mixture was refluxed and a nitrogen gas atmosphere was maintained. The final depolymerized product was 580 g.

100 g of the above-mentioned scrap depolymerized product was weighed, 455 g of pre-treated soybean oil and 41 g of PPG-400 and PPG-2070 were weighed in as a polyol, uniformly mixed at room temperature, and finally 741 g of a hybrid binder. Got. This is indicated as C-1 in Table 1 below.

Production Examples 2 to 6

580 g of the polyurethane hybrid binder was obtained by the method according to Production Example 1, and variously mixed with the composition ratios as shown in Table 1 below to obtain a final hybrid binder composition. This is represented as C-2 to C-6 in Table 1 below.

Hybrid Binder Composition Formulation Table  Example No. Polyurethane
Depolymerization (g) Pretreated Soybean Oil
(g) PPG-400
(g) PPG-2070
(g)    C-1      100      455     145      41    C-2      100      455      91     102    C-3      100      455      36     163    C-4      100      568     227      51    C-5      100      568     136     153    C-6      100      568      45     255

The hybrid binder composition according to the present invention can be cured even at normal room temperature, and can be cured without using harmful components such as isocyanates which are harmful to humans as in the prior art.

In addition, the hybrid binder composition according to the present invention, when used as a binder in the packaging material of the rubber chip to be installed outdoors, since its physical properties are inferior to the conventional urethane binder, it can be usefully used as a binder in this field.

Hereinafter, an embodiment of the specific use of the present invention will be described, and its physical properties will be described.

Application Example of the Invention

100 g of the hybrid binder composition obtained by each of the above production examples were weighed, and 2 phr of BF ₃ dietherate was added to the polypropylene glycol by weight.

At the same time, 400 g of rubber chips (manufacturer: Plubber Co., Ltd., product name: EPDM color chips, product characteristics: pellet type) were weighed, put into a mixing container, mixed, cast into a specimen mold, and cast at 100 ° C. Cured for 3 hours. This is a conventional conventional curing reaction is a compaction process using a roller at 160 ℃ compared to the generation of a large amount of isocyanate vapor, it is a relatively low temperature reaction and has the advantage that there is no fear of the generation of toxic substances.

`` Experimental measurement examples such as tensile strength of the present invention ''

The hybrid binder obtained in the above production examples was cured with a curing agent and then made into a specimen, and the rubber chip cured product, which was cured by mixing with a rubber chip according to the above applied examples, was made into a specimen and the physical properties thereof were measured.

The physical property test method of each product was based on the KS test method, and the tensile properties were tested at 50 mm / min using Lloyd's universal tensile tester Ametek. The obtained tensile test results are shown in Table 2.

Physical properties when used on rubber chips for elastic packaging  Example No. bookbinder
Tensile Strength (Mpa) bookbinder
% Elongation Composite material
Tensile Strength (MPa) Composite material
% Elongation     C-1    14.5    166     1.09    145     C-2    14.9    168     1.10    142     C-3    11.5    140     1.16    151     C-4    5.05    220     0.62    165     C-5    5.59    167     0.64    162     C-6    4.25    157     0.62    158

According to Table 2, it was confirmed that the hybrid binder composition according to the present invention can change the composition blending ratio according to the level of binder physical properties to be finally used.

For reference, the commercially available composite packaging tensile strength of 0.87 MPa and the composite elongation of 149% was confirmed that the binder performance of the present invention was found to be equivalent to the existing product.

Although the hybrid binder composition and a method of using the same according to the present invention have been described in detail, the present invention is not limited thereto, but the present invention is not limited thereto. Range is determined and defined.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope of the present invention.

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Claims (6)

100 parts by weight of the depolymerized product obtained through the depolymerization process from the polyurethane scrap;
100 to 500 parts by weight of epoxidized soybean oil;
10 to 200 parts by weight of polyol; To
A hybrid binder composition obtained by reacting at room temperature.
The method of claim 1,
The epoxidized soybean oil is a soybean oil having a large number of unsaturated double bonds, characterized in that the treatment to form an epoxy group using hydrogen peroxide or peroxide.
The method of claim 1,
The polyol is a hybrid binder composition having a hydroxyl group, at least one selected from the group consisting of ether polyol, ester polyol, caprolactone polyol, carbonate polyol, and polybutadiene polyol.
A depolymerization process in which the polyurethane scrap is reacted with a low molecular weight glycol or amine and heated to a temperature of 180 to 220 ° C. to obtain a depolymerized product firstly;
Preparing a three-component binder composition in which 100 to 500 parts by weight of epoxidized soybean oil and 10 to 200 parts by weight of polyol are added and mixed at room temperature with respect to 100 parts by weight of the depolymerized product; of
Method for producing a hybrid binder composition comprising a.
A depolymerization process in which the polyurethane scrap is reacted with a low molecular weight glycol or amine and heated to a temperature of 180 to 220 ° C. to obtain a depolymerized product firstly;
Preparing a three-component binder composition in which 100 to 500 parts by weight of epoxidized soybean oil and 10 to 200 parts by weight of polyol are added and mixed at room temperature with respect to 100 parts by weight of the depolymerized product;
Curing the three-component binder composition with a curing agent and simultaneously using the same in a rubber chip packaging material as a binder; of
A method of using a hybrid binder composition, characterized in that it comprises.
The method of claim 5, wherein
The curing agent of the hybrid binder composition, characterized in that using any one or two or more selected from the group consisting of BF ₃ , AlCl ₃ , SnCl ₄ , and TiCl ₄ .

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