Patent Application
20230382837
The present disclosure relates to a monomer composition for synthesizing recycled plastic that contains a high-purity aromatic diol compound recovered through recycling by chemical decomposition of a polycarbonate-based resin, a method for preparing the same, and a recycled plastic and molded product using the same.
Polycarbonate is a thermoplastic polymer and is a plastic having excellent characteristics such as excellent transparency, ductility, and relatively low manufacturing cost.
Although polycarbonate is widely used for various purposes, environmental and health concerns during waste treatment have been continuously raised.
Currently, a physical recycling method is carried out, but in this case, a problem accompanying the deterioration of the quality occurs, and thus, research on the chemical recycling of polycarbonate is underway.
Chemical decomposition of polycarbonate refers to obtaining an aromatic diol compound as a monomer (e.g., bisphenol A (BPA)) through decomposition of polycarbonate, and then utilizing it again in polymerization to obtain a high-purity polycarbonate.
For such a chemical decomposition, thermal decomposition, hydrolysis, and alcohol decomposition are typically known. Among these, the most common method is alcohol decomposition using a base catalyst, but in the case of methanol decomposition, there is a problem that methanol is used which is harmful to the human body, and in the case of ethanol, there is a problem that high temperature and high pressure conditions are required and the yield is not high.
In addition, although an alcohol decomposition method using an organic catalyst is known, it is disadvantageous in terms of economics.
The background description provided herein is for the purpose of generally presenting context of the disclosure. Unless otherwise indicated herein, the materials described in this section are not prior art to the claims in this application and are not admitted to be prior art, or suggestions of the prior art, by inclusion in this section.
It is an object of the present disclosure to provide a monomer composition for synthesizing recycled plastic that can secure a high-purity aromatic diol compound recovered through recycling by chemical decomposition of a polycarbonate-based resin.
It is another object of the present disclosure to provide a method for preparing the monomer composition for synthesizing recycled plastic, and a recycled plastic, and molded product using the monomer composition for synthesizing recycled plastic.
In order to achieve the above object, provided herein is a monomer composition for synthesizing recycled plastic, comprising: an aromatic diol compound, wherein a color coordinate L* of the monomer composition is more than 95, wherein a yield of the aromatic diol compound according to the following Equation 1 is 55% or more, and wherein the monomer composition is a recovered product from a polycarbonate-based resin:
Yield (%)=W1/W0 [Equation 1]
Also provided herein is a method for preparing a monomer composition for synthesizing recycled plastic, the method comprising the steps of: depolymerizing a polycarbonate-based resin; adding water of 12 times or more the weight of the polycarbonate-based resin to the depolymerization reaction product to extract an aromatic diol compound.
Further provided herein is a recycled plastic comprising a reaction product of the monomer composition and a comonomer.
Further provided herein is a molded product comprising the recycled plastic.
Below, a monomer composition for synthesizing recycled plastic, a method for preparing the same, and a recycled plastic, and molded product using the same according to specific embodiments of the present disclosure will be described in more detail.
Unless explicitly stated herein, the technical terms used herein are for the purpose of describing specific embodiments only and is not intended to limit the scope of the invention.
The singular forms “a,” “an” and “the” used herein are intended to include plural forms, unless the context clearly indicates otherwise.
It should be understood that the terms “comprise,” “include”, “have”, etc. are used herein to specify the presence of stated feature, region, integer, step, action, element and/or component, but do not preclude the presence or addition of one or more other feature, region, integer, step, action, element, component and/or group.
Further, the terms including ordinal numbers such as “a first”, “a second”, etc. are used only for the purpose of distinguishing one component from another component, and are not limited by the ordinal numbers. For instance, a first component may be referred to as a second component, or similarly, the second component may be referred to as the first component, without departing from the scope of the present disclosure.
According to one embodiment of the present disclosure, there can be provided a monomer composition for synthesizing recycled plastic, which comprises an aromatic diol compound, wherein a color coordinate L* is more than 95, wherein the aromatic diol compound yield according to the following Equation 1 is 55% or more, and wherein the monomer composition for synthesizing recycled plastic is recovered from a polycarbonate-based resin:
Yield (%)=W1/W0 [Equation 1]
The present inventors have found through experiments that although the monomer composition for synthesizing recycled plastics of the one embodiment was recovered through recycling by chemical decomposition of the polycarbonate-based resin, the aromatic diol compound, which is the main recovery target, is secured with high purity and high yield, thereby capable of realizing excellent physical properties in the synthesis of polycarbonate-based resins using the same, and completed the present disclosure.
In particular, the monomer composition (first composition) for synthesizing recycled plastics of the one embodiment, and the monomer composition (second composition) for synthesizing recycled plastic which comprises diethyl carbonate wherein the diethyl carbonate is recovered from a polycarbonate-based resin, can be respectively simultaneously obtained in a method for preparing a monomer composition for synthesizing recycled plastics, which will be described later.
That is, the present disclosure may have technical features that a first composition comprising an aromatic diol compound is obtained with high purity through recycling by chemical decomposition of polycarbonate-based resin, and at the same time, a second composition comprising diethyl carbonate as a by-product with a high added value can also be obtained.
Specifically, the monomer composition for synthesizing recycled plastics of the one embodiment is characterized by being recovered from a polycarbonate-based resin. That is, this means that recovery is performed from the polycarbonate-based resin in order to obtain the monomer composition for synthesizing recycled plastics of the one embodiment, and as a result, the monomer composition for synthesizing recycled plastics containing the aromatic diol compound is obtained together.
The polycarbonate-based resin is meant to include both a homopolymer and a copolymer containing a polycarbonate repeating unit, and collectively refers to a reaction product obtained through a polymerization reaction or a copolymerization reaction of a monomer containing an aromatic diol compound and a carbonate precursor. When it contains one carbonate repeating unit obtained by using only one aromatic diol compound and one carbonate precursor, a homopolymer can be synthesized. In addition, when one aromatic diol compound and two or more carbonate precursors are used as the monomer, or two or more aromatic diol compounds and one carbonate precursor are used, or one or more other diols is used in addition to the one aromatic diol compound and the one carbonate precursor to contain two or more carbonates, a copolymer can be synthesized. The homopolymer or copolymer can include all of low-molecular compounds, oligomers, and polymers depending on the molecular weight range.
Further, the monomer composition for synthesizing recycled plastics of the one embodiment may include an aromatic diol compound. Specific examples of the aromatic diol compound include bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis (4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z), 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis (4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis (4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, or a mixture of two or more thereof, and the like. Preferably, the aromatic diol compound of the monomer composition for synthesizing recycled plastics of the one embodiment may be 2,2-bis(4-hydroxyphenyl)propane (bisphenol A).
The aromatic diol compound is characterized by being recovered from the polycarbonate-based resin used for recovering the monomer composition for synthesizing the recycled plastic. That is, this means that recovery is performed from the polycarbonate-based resin in order to obtain the monomer composition for synthesizing recycled plastics of the one embodiment, and as a result, an aromatic diol compound is also obtained together. Therefore, apart from the recovery from the polycarbonate-based resin in order to prepare the monomer composition for synthesizing recycled plastics of the one embodiment, the case where a novel aromatic diol compound is added from the outside is not included in the category of aromatic diol compound of the present disclosure.
Specifically, “recovered from the polycarbonate-based resin” means being obtained through a depolymerization reaction of the polycarbonate-based resin. The depolymerization reaction can be carried out under acidic, neutral or basic conditions, and particularly, the depolymerization reaction can proceed under basic (alkaline) conditions. Particularly, the depolymerization reaction can be preferably carried out in the presence of an ethanol solvent, as will be described later.
Meanwhile, the monomer composition for synthesizing recycled plastics of the one embodiment may have a color coordinate b* value of 3.5 or less, or 0.1 or more, or 0.1 to 3.5, or 1.0 to 3.5, or 2.0 to 3.5, or 2.3 to 3.1. Also, the monomer composition for synthesizing recycled plastics of the one embodiment may have a color coordinate L* of more than 95, or 100 or less, or more than 95 and 100 or less, or 95.2 to 97. Further, the monomer composition for synthesizing recycled plastics of the one embodiment may have a color coordinate a* of 1 or less, or 0.1 or more, or 0.1 to 1, or 0.2 to 0.6.
As used herein, the “color coordinates” means coordinates in the CIE Lab color space, which are color values defined by CIE (Commossion International de l'Eclairage), and an arbitrary position in the CIE color space may be represented by three coordinate values, i.e., L*, a*, and b*.
Here, the L* value represents brightness, when L*=0, it represents black, and when L*=100, it represents white. In addition, the a* value represents a color having a corresponding color coordinate that leans toward one of pure red and pure green, and the b* value represents a color having a corresponding color coordinate that leans toward one of pure yellow and pure blue.
Specifically, the a* value is in the range of −a to +a. A maximum value of a* (a* max) represents pure red, and a minimum value of a* (a* min) represents pure green. Further, the b* value is in the range of −b to +b. A maximum value of b* (b* max) represents pure yellow, and a minimum value of b* (b* min) represents pure blue. For example, a negative b* value represents a color leaning toward pure blue, and a positive b* value represents color leaning toward pure yellow. When comparing b*=50 with b*=80, b*=80 is closer to pure yellow than b*=50.
When the color coordinate b* value of the monomer composition for synthesizing recycled plastics of the one embodiment excessively increases to more than 3.5, or the color coordinate L* value excessively decreases to less than 95, or the color coordinate a* value excessively increases to more than 1, the monomer composition for synthesizing recycled plastics of the one embodiment deteriorates in the color characteristics.
Examples of the method for measuring the color coordinates L*, a*, b* values of the monomer composition for synthesizing recycled plastics of the one embodiment are not particularly limited, and various color characteristic measurement methods in the field of plastics can be applied without limitation.
However, the color coordinates L*, a*, and b* values of the monomer composition for synthesizing recycled plastics of the one embodiment can be measured in reflection mode using HunterLab UltraScan PRO Spectrophotometer as an example.
Meanwhile, the monomer composition for synthesizing recycled plastics of the one embodiment may have an aromatic diol compound yield of 55% or more, or 100% or less, or 55% to 100%, or 55% to 70%. Increasing the yield of the aromatic diol compound to 55% or more is considered to be due to the inclusion of a step of adding water of 12 times or more the weight of the polycarbonate-based resin to the depolymerization reaction product to extract the aromatic diol compound in the method for preparing a monomer composition for synthesizing recycled plastics, which will be described later.
An example of a method for measuring the yield of the aromatic diol compound of the monomer composition for synthesizing recycled plastics of the one embodiment is not particularly limited, and for example, the yield can be calculated through the following Equation 1.
Yield (%)=W1/W0 [Equation 1]
For the measurement of the mass of the aromatic diol compound in Equation 1, various well-known mass measurement methods can be used without limitation, and for example, a scale can be used.
Thus, in the monomer composition for synthesizing recycled plastics of the one embodiment, the yield of the aromatic diol compound, which is the main recovery target material, is remarkably increased to 55% or more, so that the efficiency of the recycling process for the polycarbonate-based resin can be improved.
Meanwhile, the monomer composition for synthesizing recycled plastics of the one embodiment may have an aromatic diol compound purity of 98% or more, or 100% or less, or 98% to 100%.
Examples of the method for measuring the purity of the aromatic diol compound of the monomer composition for synthesizing recycled plastics of the one embodiment are not particularly limited, and for example, 1H NMR, ICP-MS analysis, HPLC analysis, UPLC analysis, etc. can be used without limitation. As for the specific methods, conditions, equipment, etc. of the NMR, ICP-MS, HPLC, and UPLC, various well-known contents can be applied without limitation.
An example of a method for measuring the purity of the aromatic diol compound of the monomer composition for synthesizing recycled plastics of the one embodiment is follows. 1 wt % of the monomer composition for synthesizing recycled plastics of the one embodiment was dissolved in acetonitrile (ACN) solvent under normal pressure and to 30° C. conditions, and then the purity of bisphenol A (BPA) was analyzed by ultraperformance liquid chromatography (UPLC) on a Waters HPLC system using ACQUITY UPLC®BEH C18 1.7 μm (2.1*50 mm column)
As described above, in the monomer composition for synthesizing recycled plastics of the one embodiment, the purity of the aromatic diol compound, which is the main recovery target material, is remarkably increased to 98% or more, and other impurities are minimized, thereby capable of achieving excellent physical properties when synthesizing a polycarbonate-based resin using the same.
Meanwhile, in the monomer composition for synthesizing recycled plastics of the one embodiment, diethyl carbonate can be obtained as a by-product. The diethyl carbonate is characterized by being recovered from the polycarbonate-based resin used for recovering the monomer composition for synthesizing recycled plastics of the one embodiment.
That is, this means that recovery is performed from the polycarbonate-based resin in order to obtain the monomer composition for synthesizing recycled plastics of the one embodiment, and as a result, diethyl carbonate is also obtained together. Therefore, apart from the recovery from the polycarbonate-based resin in order to prepare the monomer composition for synthesizing recycled plastics of the one embodiment, the case where a novel diethyl carbonate is added from the outside is not included in the category of diethyl carbonate of the present disclosure.
Specifically, “recovered from the polycarbonate-based resin” means being obtained through a depolymerization reaction of the polycarbonate-based resin. The depolymerization reaction can be carried out under acidic, neutral or basic conditions, and particularly, the depolymerization reaction can proceed under basic (alkaline) conditions. Particularly, the depolymerization reaction can be preferably carried out in the presence of an ethanol solvent, as will be described later.
Since the main recovery target material in the monomer composition for synthesizing recycled plastics of the one embodiment is an aromatic diol compound, the diethyl carbonate can be separately separated and recovered as the by-product from the monomer composition for synthesizing recycled plastics of the one embodiment.
The monomer composition for synthesizing recycled plastics of the one embodiment can be used as a raw material for preparing various recycled plastics (e.g., polycarbonate (PC)) which will be described later.
The monomer composition for synthesizing recycled plastics of the one embodiment may further include small amounts of other additives and solvents. Specific types of the additives or solvents are not particularly limited, and various materials widely used in the process of recovering the aromatic diol compound by a depolymerization of the polycarbonate-based resin can be applied without limitation.
The monomer composition for synthesizing recycled plastics of the one embodiment can be obtained by a method for preparing a monomer composition for synthesizing recycled plastics, which will be described later. That is, the monomer composition for synthesizing recycled plastics of one embodiment corresponds to the result obtained through various processes of filtration, purification, washing, and drying in order to secure only the aromatic diol compound, which is the main recovery target material, with high purity after the depolymerization reaction of the polycarbonate-based resin.
According to another embodiment of the present disclosure, there can be provided a method for preparing a monomer composition for synthesizing recycled plastic, the method comprising the steps of: depolymerizing a polycarbonate-based resin; and adding water of 12 times or more the weight of the polycarbonate-based resin to the depolymerization reaction product to extract the aromatic diol compound.
The present inventors confirmed through experiments that similarly to the method for preparing the monomer composition for synthesizing recycled plastic of the other embodiments, an aromatic diol compound is extracted using a specific content of water in the process of recycling the polycarbonate-based resin by chemical decomposition, whereby the aromatic diol compound, which is the main synthesis target material in the present disclosure, can be secured with high purity, and completed the present disclosure.
Specifically, the method for preparing the monomer composition for synthesizing recycled plastics of the other embodiment may comprise a step of depolymerizing a polycarbonate-based resin.
The polycarbonate-based resin is meant to include both a homopolymer and a copolymer containing a polycarbonate repeating unit, and collectively refers to a reaction product obtained through a polymerization reaction or a copolymerization reaction of a monomer containing an aromatic diol compound and a carbonate precursor. When it contains one carbonate repeating unit obtained by using only one aromatic diol compound and one carbonate precursor, a homopolymer can be synthesized. In addition, when one aromatic diol compound and two or more carbonate precursors are used as the monomer, or two or more aromatic diol compounds and one carbonate precursor are used, or one or more other diols is used in addition to the one aromatic diol compound and the one carbonate precursor to contain two or more carbonates, a copolymer can be synthesized. The homopolymer or copolymer can include all of low-molecular compounds, oligomers, and polymers depending on the molecular weight range.
The polycarbonate-based resin can be applied regardless of various forms and types, such as a novel polycarbonate-based resin produced through synthesis, a recycled polycarbonate-based resin produced through a regeneration process, or polycarbonate-based resin waste.
However, if necessary, before proceeding the depolymerization reaction of the polycarbonate-based resin, a pretreatment step of the polycarbonate-based resin is carried out, thereby capable of increasing the efficiency of the process of recovering the aromatic diol compound and the carbonate precursor from the polycarbonate-based resin. Examples of the pretreatment process may include washing, drying, grinding, glycol decomposition, and the like. The specific method of each pretreatment process is not limited, and various methods widely used in the process of recovering the aromatic diol compound and the carbonate precursor from the polycarbonate-based resin can be applied without limitation.
During the depolymerization reaction of the polycarbonate-based resin, the depolymerization reaction may be carried out under acidic, neutral or basic conditions, and particularly, the depolymerization reaction may be carried out under basic (alkali) conditions. The type of the base is not particularly limited, and examples thereof include sodium hydroxide (NaOH) or potassium hydroxide (KOH). The base is a base catalyst acting as a catalyst, and has the economic advantages over organic catalysts, which are mainly used under mild conditions.
During the depolymerization reaction of the polycarbonate-based resin, the depolymerization reaction may be carried out by reacting a base in an amount of 0.5 mol or less, or 0.4 moles or less, or 0.3 moles or less, or 0.1 moles or more, or 0.2 mole or more, or 0.1 mole to 0.5 mole, or 0.1 mole to 0.4 mole, or 0.1 mole to 0.3 mole, or 0.2 mole to 0.5 mole, or 0.2 mole to 0.4 mole, or 0.2 mole to 0.3 mole relative to 1 mole of polycarbonate-based resin. When the polycarbonate-based resin is reacted with a base in an amount of more than 0.5 mol relative to 1 mole of the polycarbonate-based resin during depolymerization of the polycarbonate-based resin, it is limited that impurities increase due to the effect of increasing the amount of alkali salt generated, so the purity of the target recovery material is reduced, and the economic efficiency of the catalytic reaction is reduced.
Further, the depolymerization reaction of the polycarbonate-based resin can be carried out in the presence of a solvent containing ethanol. The present disclosure can stably obtain bisphenol A, which is a high-purity monomer, by decomposing a polycarbonate-based resin with a solvent containing ethanol, and has the advantage that diethyl carbonate having a high added value can be further obtained as a reaction by-product.
The content of the ethanol may be 5 to 15 moles, or 8 to 13 moles relative to 1 mole of the polycarbonate-based resin. Since the ethanol has good solubility in bisphenol A, ethanol within the above range should be essentially contained. When the content of the ethanol is excessively reduced to less than 5 moles relative to 1 mole of the polycarbonate-based resin, it is difficult to sufficiently progress the alcohol decomposition of polycarbonate-based resin. On the other hand, when the content of ethanol is excessively increased to more than 15 moles relative to 1 mole of the polycarbonate-based resin, the economics of the process can be reduced due to excessive use of alcohol.
The solvent in which the depolymerization reaction of the polycarbonate-based resin proceeds may further include, in addition to ethanol, at least one organic solvent selected from the group consisting of tetrahydrofuran, toluene, methylene chloride, chloroform, dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, and dipropyl carbonate.
The organic solvent may include tetrahydrofuran, toluene, methylene chloride, chloroform, dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, dipropyl carbonate, or a mixture of two or more thereof.
More preferably, methylene chloride can be used as the organic solvent. When methylene chloride is used as an organic solvent to be mixed with the ethanol, there is an advantage that the dissolution properties in polycarbonate can be improved and the reactivity can be improved.
The content of the organic solvent may be 16 moles to 20 moles, or 16 moles to 18 moles relative to 1 mole of the polycarbonate-based resin. In addition, the content of the organic solvent may be 1.5 moles to 2 moles relative to total 1 mole of ethanol. By mixing the polycarbonate-based resin, ethanol, and an organic solvent within the above range, there is an advantage that the depolymerization reaction of the polymer can proceed at a desired level.
Meanwhile, the temperature at which the depolymerization reaction of the polycarbonate-based resin proceeds is not particularly limited, but for example, the reaction may proceed at a temperature of 20° C. to 100° C., or 50° C. to 70° C. In addition, the depolymerization of the polycarbonate-based resin may proceed for 1 hour to 30 hours, or 4 hours to 6 hours.
In particular, when stirring at 50° C. to 70° C. for 4 to 6 hours, there is an advantage of obtaining the most efficient results in terms of reproducibility and acceptability.
That is, according to the present disclosure, by adjusting the type and mixing amount of the mixed solvent and the type and content of the base catalyst without using an organic catalyst, there is the advantage that a high-purity aromatic diol compound (e.g., bisphenol A) can be obtained under mild conditions without using a pressure/high temperature process, and diethyl carbonate can be obtained as a by-product by using an ethanol solvent.
More specifically, the step of depolymerizing the polycarbonate-based resin may include a first step of dissolving the carbonate-based resin in an organic solvent; and a second step of adding and stirring a catalyst solution containing ethanol and a base. In the first and second steps, the contents of ethanol, organic solvent, base, and polycarbonate-based resin are the same as described above.
Meanwhile, the method for preparing the monomer composition for synthesizing recycled plastics of the other embodiment may further include a step of neutralizing the depolymerization reaction product with an acid, before the step of adding an adsorbent to the depolymerization reaction product to perform an adsorption purification and then removing the adsorbent, which will be described later.
For example, the alkali decomposition product of the polycarbonate-based resin includes an aromatic diol compound, or a salt thereof, but the main recovery target material of the present disclosure is an aromatic diol compound. Therefore, in the case of the salt of the aromatic diol compound obtained by alkaline decomposition, it can be converted into an aromatic diol compound through an additional acid neutralization process. That is, when the depolymerization reaction of the polycarbonate-based resin is an alkaline decomposition, it can undergo a neutralization reaction step with an acid.
The acid used in the neutralization reaction may be a strong acid, for example, hydrochloric acid (HCl). Due to the neutralization reaction by the strong acid, the pH can satisfy 4 or less, or 2 or less upon completion of the neutralization reaction. The temperature during the neutralization reaction can be adjusted to 25° C. or more and 100° C. or less.
Further, if necessary, after proceeding the neutralization reaction step of the depolymerization reaction product by an acid, a step of removing residual impurities through filtration or absorption can be further performed. Specifically, the aqueous layer and the organic layer can be separated, and the organic layer can be filtered through vacuum filtration to recover the liquid containing the aromatic diol compound.
Meanwhile, the method for preparing the monomer composition for synthesizing recycled plastics of the other embodiment may include a step of adding an adsorbent to the depolymerization reaction product to perform an adsorption purification and then removing the adsorbent, before the step of adding water of 12 times or more the weight of the polycarbonate-based resin to the depolymerization reaction product to extract the aromatic diol compound. In the step of adding an adsorbent to the depolymerization reaction product to perform an adsorption purification and then removing the adsorbent, an adsorbent can be brought into contact with the depolymerization reaction product.
Examples of the adsorbent that can be used include activated carbon, charcoal, or a mixture thereof. The activated carbon is a black carbon material having micropores produced by subjecting a raw material to a carbonization process at about 500° C. and an activated carbon process at about 900° C., and examples thereof are not particularly limited, but for example, various activated carbons such as plant-based, coal-based, petroleum-based, waste-based activated carbon can be applied without limitation depending on the type of raw material.
In more specific examples, the plant-based activated carbon may include coconut activated carbon, wood activated carbon, and sawdust activated carbon. Further, the coal-based activated carbon may include lignite activated carbon, bituminous coal activated carbon, and anthracite activated carbon. Further, the petroleum-based activated carbon may include petroleum coke activated carbon and oil carbon activated carbon. Further, the waste activated carbon may include synthetic resin activated carbon and pulp activated carbon.
The adsorbent may include at least one activated carbon selected from the group consisting of plant-based activated carbon, coal-based activated carbon, petroleum-based activated carbon, and waste-based activated carbon. That is, the adsorbent may include plant-based activated carbon, coal-based activated carbon, petroleum-based activated carbon, waste-based activated carbon, or a mixture of two or more thereof.
More specifically, the adsorbent may include at least one activated carbon selected from the group consisting of coconut activated carbon, lignite activated carbon, anthracite activated carbon, and bituminous coal activated carbon. That is, the adsorbent may include coconut activated carbon, lignite activated carbon, anthracite activated carbon, bituminous coal activated carbon, or a mixture of two or more thereof.
Adsorption purification conditions by the adsorbent are not particularly limited, and various well-known adsorption purification conditions can be used without limitation. However, as an example, the addition amount of the adsorbent may be 40% to 60% by weight relative to the polycarbonate-based resin, and the adsorption time may be 1 hour to 5 hours, and the adsorption method may be a stirring adsorption or an adsorption tower for Lab.
Meanwhile, the method for preparing the monomer composition for synthesizing recycled plastics of the other embodiment may include a step of adding water of 12 times or more the weight of the polycarbonate-based resin to the depolymerization reaction product to extract the aromatic diol compound. As the aromatic diol compound is extracted using a specific amount of water in this way, the aromatic diol compound, which is the main synthetic target material in the present disclosure, can be obtained with in high purity and high yield.
As shown in
For example, the depolymerization reaction product of the polycarbonate-based resin includes an aromatic diol compound or a salt thereof and a carbonate precursor. The contents related to the aromatic diol compound and the carbonate precursor include all the contents described above in the one embodiment.
Water can be added to the depolymerization reaction product in an amount of 12 times or more, or 13 times or more, or 14 times or more, or 15 times or more, or 16 times or more, or 20 times or less, or 12 times to 20 times, or 13 times to 20 times, or 14 times to 20 times, or 15 times to 20 times, or 16times to 20 times the weight of the polycarbonate-based resin to extract an aromatic diol compound.
That is, assuming that the weight of the polycarbonate-based resin is 100 g as an example, 1200 g or more of water, which is 12 times the weight of the polycarbonate-based resin, may be added during extraction of the aromatic diol compound.
When the amount of water added during extraction of the aromatic diol compound is excessively reduced to less than 12 times the weight of the polycarbonate-based resin, the aromatic diol compound may not be sufficiently extracted and thus, the yield may decrease. On the other hand, when the amount of water added during extraction of the aromatic diol compound is excessively increased to more than 20 times the weight of the polycarbonate-based resin, excess water may be required, which may reduce the efficiency of the extraction process.
Specifically, in the step of adding water in an amount of 12 times or more the weight of the polycarbonate-based resin to the depolymerization reaction product to extract the aromatic diol compound, the number of times of adding water may be 1 to 10 times, or 2 to 10 times, or 3 to 10 times, or 4 to 10 times, or 1 to 8 times, or 2 to 8 times, or 3 to 8 times, or 4 to 8 times.
If the number of times of adding the water is 2 times or more, water is repeatedly added, and when water is added repeatedly 2 to 10 times, the method may further include a step of removing water between the steps of adding water.
More specifically, the step of adding water of 12 times or more the weight of the polycarbonate-based resin to the depolymerization reaction product to extract the aromatic diol compound may include repeatedly adding water of twice the weight of the polycarbonate-based resin to the depolymerization product 6 to 10 times, or 6 to 8 times.
Further, the step of adding water of 12 times or more the weight of the polycarbonate-based resin to the depolymerization reaction product to extract the aromatic diol compound may include repeatedly adding water of 4 times the weight of the polycarbonate-based resin to the depolymerization product 3 to 5 times, or 3 to 6 times.
The step of adding water of 12 times or more the weight of the polycarbonate-based resin to the depolymerization reaction product to extract the aromatic diol compound may include a step of adding water of 12 times the weight of the polycarbonate-based resin to the depolymerization product once.
Meanwhile, the method for preparing the monomer composition for synthesizing recycled plastics of the other embodiment may include a step of purifying the extracted aromatic diol compound. Thereby, an aromatic diol compound, which is the main recovered material, is obtained, which corresponds to the monomer composition for synthesizing recycled plastic according to the one embodiment.
Specifically, the purification step of the extracted aromatic diol compound may include a washing step of the extracted aromatic diol compound.
Specifically, in the washing step of the extracted aromatic diol compound, since various impurities remain in the extracted aromatic diol compound during the recovery process for obtaining it, washing can be performed in order to sufficiently remove these impurities and secure a high-purity aromatic diol compound.
Specifically, the washing step may include a step of washing with a solvent at a temperature of 10° C. or more and 30° C. or less, or 20° C. or more and 30° C. or less; and a step of washing with a solvent at a temperature of 40° C. or more and 80° C. or less, or 40° C. or more and 60° C. or less, or 45° C. or more and 55° C. or less. The temperature condition means the temperature inside the washing container at which washing with a solvent is performed. In order to maintain a high temperature deviating from a room temperature, various heating devices can be applied without limitation.
In the washing step, the step of washing with a solvent at a temperature of 10° C. or more and 30° C. or less may be performed first, and the step of washing with a solvent at a temperature of 40° C. or more and 80° C. or less may be performed later. Alternatively, the step of washing with a solvent at a temperature of 40° C. or more and 80° C. or less may be performed first, and the step of washing with a solvent at a temperature of 10° C. or more and 30° C. or less may be performed later.
More preferably, in the washing step, the step of washing with a solvent at a temperature of 10° C. or more and 30° C. or less may be performed first, and the step of washing with a solvent at a temperature of 40° C. or more and 80° C. or less may be performed later. Thereby, the corrosion of the reactor due to strong acid after the neutralization step can be minimized
The step of washing with a solvent at a temperature of 10° C. or more and 30° C. or less; and the step of washing with a solvent at a temperature of 40° C. or more and 80° C. or less can be repeated at least once or more, respectively.
Further, if necessary, after proceeding the step of washing with a solvent at a temperature of 10° C. or more and 30° C. or less; and the step of washing with a solvent at a temperature of 40° C. or more and 80° C. or less, a step of removing the residual solvent through filtration may be further performed.
More specifically, the difference value between the temperature of the step of washing with a solvent at a temperature of 40° C. or more and 80° C. or less and the temperature of the step of washing with a solvent at a temperature of 10° C. or more and or less may be 20° C. or more and 50° C. or less.
The difference value between the temperature of the step of washing with a solvent at a temperature of 40° C. or more and 80° C. or less and the temperature of the step of washing with a solvent at a temperature of 10° C. or more and 30° C. or less means a value obtained by subtracting the temperature of the step of washing with a solvent at a temperature of 10° C. or more and 30° C. or less from the temperature of the step of washing with a solvent at a temperature of 40° C. or more and 80° C. or less.
When the difference value between the temperature of the step of washing with a solvent at a temperature of 40° C. or more and 80° C. or less and the temperature of the step of washing with a solvent at a temperature of 10° C. or more and 30° C. or less decreases excessively to less than 20° C., it is difficult to sufficiently remove impurities.
When the difference value between the temperature of the step of washing with a solvent at a temperature of 40° C. or more and 80° C. or less and the temperature of the step of washing with a solvent at a temperature of 10° C. or more and 30° C. or less increases excessively to more than 50° C., severe conditions are formed in order to maintain extreme temperature conditions, which can reduce the efficiency of the process.
The solvent used in the washing step may include one of water, alcohol, and an organic solvent. As the organic solvent, tetrahydrofuran, toluene, methylene chloride, chloroform, dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, dipropyl carbonate, or a mixture of two or more thereof can be used.
The solvent used in the washing step can be used in a weight ratio of 1 part by weight or more and 30 parts by weight or less, or 1 part by weight or more and 10 parts by weight or less based on 1 part by weight of the polycarbonate-based resin used in the depolymerization reaction.
More specifically, the solvent in the step of washing with a solvent at a temperature of 10° C. or more and 30° C. or less may be an organic solvent. Preferably, methylene chloride can be used as the organic solvent. At this time, the organic solvent can be used in an amount of 1 part by weight or more and 10 parts by weight or less based on 1 part by weight of the polycarbonate-based resin.
Moreover, the solvent in the step of washing with a solvent at a temperature of or more and 80° C. or less may be water. When water is used, impurities in the form of residual salts can be effectively removed. At this time, the solvent can be used in an amount of 1 part by weight or more and 10 parts by weight or less based on 1 part by weight of the polycarbonate-based resin.
Further, if necessary, a drying step can be further included , after the washing step. The residual solvent can be removed through the drying, and specific drying conditions are not particularly limited, but for example, drying may be performed at a temperature of 10° C. to 100° C., or 10° C. to 50° C. As for the specific drying equipment and method used in the drying, various well-known drying techniques can be applied without limitation.
According to another embodiment of the present disclosure, a recycled plastic comprising a reaction product of the monomer composition for synthesizing recycled plastic of the one embodiment and a comonomer can be provided.
The details of the monomer composition for synthesizing recycled plastic of the one embodiment include all the contents described above in the one embodiment and the other embodiment.
Examples corresponding to the recycled plastic are not particularly limited, and various plastics synthesized from aromatic diol compounds such as bisphenol A as a monomer can be applied without limitation, and a more specific example may be a polycarbonate-based resin.
The polycarbonate-based resin is meant to include both a homopolymer and a copolymer containing a polycarbonate repeating unit, and collectively refers to a reaction product obtained through a polymerization reaction or a copolymerization reaction of a monomer containing an aromatic diol compound and a carbonate precursor. When it contains one carbonate repeating unit obtained by using only one aromatic diol compound and one carbonate precursor, a homopolymer can be synthesized. In addition, when one aromatic diol compound and two or more carbonate precursors are used as the monomer, or two or more aromatic diol compounds and one carbonate precursor are used, or one or more other diols is used in addition to the one aromatic diol compound and the one carbonate precursor to contain two or more carbonates, a copolymer can be synthesized. The homopolymer or copolymer can include all of low-molecular compounds, oligomers, and polymers depending on the molecular weight range.
More specifically, in the recycled plastic containing the reaction product of the monomer composition for synthesizing the recycled plastic and the comonomer of the one embodiment, a carbonate precursor can be used as the comonomer. Specific examples of the carbonate precursor include phosgene, triphosgene, diphosgene, bromophosgene, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl)carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate or bishaloformate.
Examples of the reaction process of the monomer composition for synthesis and the comonomer are not particularly limited, and various well-known methods for preparing polycarbonate can be applied without limitation.
However, in one example of the polycarbonate preparation method, a polycarbonate preparation method including the step of polymerizing a composition containing a monomer composition for synthesizing recycled plastic and a comonomer can be used. At this time, the polymerization can be carried out by interfacial polymerization, and during interfacial polymerization, polymerization reaction is possible at normal pressure and low temperature, and the molecular weight is easy to control.
The polymerization temperature may be 0° C. to 40° C., and the reaction time may be 10 minutes to 5 hours. In addition, the pH during the reaction may be maintained at 9 or more or 11 or more.
The solvent that can be used for the polymerization is not particularly limited as long as it is a solvent used for polymerization of polycarbonate in the art, and as an example, halogenated hydrocarbons such as methylene chloride and chlorobenzene can be used.
Moreover, the polymerization can be carried out in the presence of an acid binder. As the acid binder, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an amine compound such as pyridine can be used.
Further, in order to control the molecular weight of the polycarbonate during the polymerization, polymerization can be performed in the presence of a molecular weight modifier. An alkylphenol having 1 to 20 carbon atoms may be used as the molecular weight modifier, and specific examples thereof include p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol or triacontylphenol. The molecular weight modifier can be added before, during or after the initiation of polymerization. The molecular weight modifier may be used in an amount of 0.01 to 10 parts by weight, or 0.1 to 6 parts by weight, based on 100 parts by weight of the aromatic diol compound, and a desired molecular weight can be obtained within this range.
In addition, in order to promote the polymerization reaction, a reaction accelerator such as a tertiary amine compound, a quaternary ammonium compound, or a quaternary phosphonium compound, including triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide can be further used.
According to another embodiment of the present disclosure, a molded article comprising the recycled plastic of the other embodiment can be provided. The details of the recycled plastic includes all the contents described above in the other embodiments.
The molded article can be obtained by applying the recycled plastic to various known plastic molding methods without limitation. As an example of the molding method, injection molding, foam injection molding, blow molding, or extrusion molding may be mentioned.
Examples of the molded article are not particularly limited, and can be applied to various molded articles using plastic without limitation. Examples of the molded article include automobiles, electrical and electronic products, communication products, daily necessities, building materials, optical components, exterior materials, and the like.
The molded article may further include one or more additives selected from the group consisting of an antioxidant, a plasticizer, an antistatic agent, a nucleating agent, a flame retardant, a lubricant, an impact enhancer, an optical brightener, an ultraviolet absorber, a pigment and a dye, if necessary, in addition to the recycled plastic of the other embodiments,
An example of the manufacturing method of the molded article may include a step of mixing the recycled plastic of the other embodiment and an additive well using a mixer, extrusion-molding the mixture with an extruder to produce pellets, drying the pellets, and then injecting them with an injection molding machine.
According to the present disclosure, a monomer composition for synthesizing recycled plastic that contains a high-purity aromatic diol compound recovered through recycling by chemical decomposition of a polycarbonate-based resin, a method for preparing the same, and a recycled plastic and molded product using the same can be provided.
Hereinafter, the present disclosure will be explained in detail with reference to the following examples. However, these examples are for illustrative purposes only, and the scope of the present disclosure is not limited thereto.
(1. Decomposition step) 1 mol of Pretreated waste polycarbonate (PC) was dissolved in 17 mol of methylene chloride (MC), and then added together with 11 mol of ethanol (EtOH) and 0.25 mol of sodium hydroxide (NaOH) to a 3 L high-pressure reactor, and the mixture was stirred at 60° C. for 6 hours to proceed a PC depolymerization reaction.
(2. Neutralization stage) The depolymerization reaction product was cooled to 30° C. or less, and then the product containing bisphenol A was neutralized using 0.25 mol of 10% hydrochloric acid (HCl) at 20˜30° C.
(3-1. Purification-Adsorption step) After that, in the product whose pH has been lowered to less than 2, charcoal as an adsorbent was added at a ratio of 50 wt % relative to waste polycarbonate, purified through adsorption for 3 hours, and then filtrated using Celite to remove the absorbent.
(3-2. Purification-Extraction step) After that, the extraction process of adding water of twice the weight of waste polycarbonate, stirring the mixture and then then removing the aqueous layer was repeated 5 times. Water of twice the weight of waste polycarbonate was added once more, and immediately, crystallized bisphenol A (BPA) was formed between the aqueous layer and the MC layer, and bisphenol A (BPA) was recovered through vacuum filtration.
(3-3. Purification-Washing step) After that, the residue from which diethyl carbonate (DEC) was removed was primarily washed using methylene chloride (MC) (1 time the mass of PC used) at 20 to 30° C., and vacuum filtered. The filtrate was secondarily washed using water (three times the mass of PC used) at a temperature of 50° C.
(4. Drying step) After that, it was dried in a vacuum oven at 40° C. to prepare a recycled bisphenol A monomer composition in which recycled bisphenol A (BPA) was recovered.
A recycled bisphenol A monomer composition was prepared in the same manner as in Example 1, except that in the (3-2. Purification-Extraction step) of Example 1, the extraction process of adding water of twice the weight of waste polycarbonate, stirring the mixture and then then removing the aqueous layer was repeated 6 times, and water of twice the weight of waste polycarbonate was added once more.
A recycled bisphenol A monomer composition was prepared in the same manner as in Example 1, except that in the (3-2. Purification-Extraction step) of Example 1, the extraction process of adding water of twice the weight of waste polycarbonate, stirring the mixture and then then removing the aqueous layer was repeated 7 times, and water of twice the weight of waste polycarbonate was added once more.
A recycled bisphenol A monomer composition was prepared in the same manner as in Example 1, except that in the (3-2. Purification-Extraction step) of Example 1, the extraction process of adding water of 4 times the weight of waste polycarbonate, stirring the mixture and then then removing the aqueous layer was repeated 2 times, and water of 4 times the weight of waste polycarbonate was added once more.
A recycled bisphenol A monomer composition was prepared in the same manner as in Example 1, except that in the (3-2. Purification-Extraction step) of Example 1, water of 12 times the weight of waste polycarbonate was added and stirred, then crystallized bisphenol A (BPA) was formed between the aqueous layer and the MC layer, and bisphenol A (BPA) was recovered through vacuum filtration.
A recycled bisphenol A monomer composition was prepared in the same manner as in Example 1, except that in the (3-2. Purification-Extraction step) of Example 1, the extraction process of adding water of twice the weight of waste polycarbonate, stirring the mixture and then then removing the aqueous layer was repeated 4 times, water of twice the weight of waste polycarbonate was added once more, and the mixture was allowed to stand for 4 to 5 hours.
A recycled bisphenol A monomer composition was prepared in the same manner as in Example 1, except that in the (3-2. Purification-Extraction step) of Example 4, the extraction process of adding water of 4 times the weight of waste polycarbonate, stirring the mixture and then then removing the aqueous layer was performed once, water of 4 times the weight of waste polycarbonate was added once more, and the mixture was allowed to stand for 4 to 5 hours.
The physical properties of the recycled bisphenol A monomer compositions obtained in the Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1 below.
1 wt % of the recycled bisphenol A monomer composition was dissolved in acetonitrile (ACN) solvent under normal pressure and 20 to 30° C. conditions, and then the purity of bisphenol A (BPA) was analyzed by ultraperformance liquid chromatography (UPLC) on a Waters HPLC system using ACQUITY UPLC®BEH C18 1.7 μm (2.1*50 mm column).
The color coordinates of the recycled bisphenol A monomer compositions were analyzed in reflection mode using HunterLab UltraScan PRO Spectrophotometer.
The weight of BPA produced during 100% decomposition of the polycarbonate used in the reaction was measured, the weight of the obtained BPA was measured, and the yield of BPA was calculated according to the following Equation 1.
Yield (%)=W1/W0 [Equation 1]
As shown in Table 1, the recycled bisphenol A monomer compositions obtained in Examples 1 to 5 exhibited high purity of 98% to 99.3%. Also, the recycled bisphenol A monomer compositions obtained in Examples 1 to 5 exhibited a color coordinates L* of 95.22 to 96.11, a* of 0.29 to 0.54, and b* of 2.33 to 3.07, showing excellent optical properties. In addition, the recycled bisphenol A monomer compositions obtained in Examples 1 to 5 were measured to have a BPA yield of 59% to 69%. On the other hand, the recycled bisphenol A monomer composition obtained in Comparative Examples 1 and 2 had a BPA yield of 42% to 50%, which was decreased compared to that of Examples.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2021-0122001 | Sep 2021 | KR | national |
| 10-2021-0122002 | Sep 2021 | KR | national |
| 10-2021-0122003 | Sep 2021 | KR | national |
| 10-2021-0122004 | Sep 2021 | KR | national |
| 10-2021-0128892 | Sep 2021 | KR | national |
| 10-2021-0136153 | Oct 2021 | KR | national |
This application is a National Phase entry pursuant to 35 U.S.C. § 371 of International Application No. PCT/KR2022/010313, filed on Jul. 14, 2022, and claims priority to and the benefit of Korean Patent Application No. 10-2021-0122001, filed on Sep. 13, 2021, Korean Patent Application No. 10-2021-0122002, filed on Sep. 13, 2021, Korean Patent Application No. 10-2021-0122003, filed on Sep. 13, 2021, Korean Patent Application No. 10-2021-0122004, filed on Sep. 13, 2021, Korean Patent Application No. 10-2021-0128892, filed on Sep. 29, 2021, and Korean Patent Application No. 10-2021-0136153, filed on Oct. 13, 2021 in the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2022/010313 | 7/14/2022 | WO |
