WO2022240253A1

WO2022240253A1 - Recycled polyvinyl chloride material

Info

Publication number: WO2022240253A1
Application number: PCT/KR2022/006921
Authority: WO
Inventors: 장명근; 이봄; 정승문; 이진규
Original assignee: (주)엘엑스하우시스
Priority date: 2021-05-14
Filing date: 2022-05-13
Publication date: 2022-11-17

Abstract

The present invention relates to a recycled PVC material and a method for manufacturing same. The method for manufacturing recycled PVC according to the present invention may be a method for recycling PVC from waste materials. The present invention may provide: a recycled PVC material recycled from waste materials and having the same physical properties as PVC material that has yet to be used, wherein unnecessary impurities such as heavy metals have been effectively removed from the recycled PVC material while beneficial additives remain; and a method for manufacturing the same. Further, the present invention makes it possible to obtain the recycled PVC material economically by using an eco-friendly process that consumes little energy.

Description

Recycled polyvinyl chloride material

This application relates to a recycled polyvinyl chloride material or a manufacturing method thereof.

The need for technology to recover plastics from waste materials is increasing. The core of plastic recovery technology to date is how purely desired plastic can be recovered from waste materials, that is, how effectively other unnecessary components other than the desired components can be removed, and how similar physical properties of recovered recycled plastic to plastic before use are. It was possible to have a .

It is required to recover plastics with physical properties equivalent to those of pre-use plastics from waste materials without impurities. Recycling plastic recovery technology also needs to be carried out as an eco-friendly, economical, and low-energy process as possible.

BACKGROUND OF THE INVENTION Poly(vinyl chloride) (hereinafter referred to as "PVC")-based materials are widely used in various products. For example, PVC-based materials are used to manufacture building materials such as windows, wallpaper, and flooring, pipes, automobile parts, hoses, agricultural films used for house cultivation of vegetables and fruits, or construction sheets.

The reason why PVC-based materials are widely used in various fields is that PVC has a property of mixing well with various materials such as plasticizers, heat stabilizers, or fillers, so that it is easy to impart desired properties and to easily color in desired colors.

However, the characteristics of being easily mixed with various materials and easily colored as above make it difficult to obtain pure PVC without impurities in the regeneration process. For example, waste materials containing PVC may contain heavy metals. This is because in the past, when applying materials containing PVC, there were no restrictions on whether or not heavy metals were included, or the current strict standards were not applied. Therefore, when PVC is recycled, it is necessary to effectively remove heavy metals contained in waste materials. However, since PVC has a property of being well mixed with other materials, it is not easy to effectively remove impurities such as heavy metals.

On the other hand, although PVC has various advantages as described above, it also has disadvantages of being rather hard and brittle.

Therefore, when PVC is applied, additives that make the PVC material flexible and do not break easily may be added to compensate for the above disadvantages, and it is advantageous that these additives are included in the recycled PVC material.

However, a selective regeneration method that removes unnecessary impurities such as heavy metals while leaving beneficial additives has not been known to date.

This application is directed to recycled PVC materials and methods for their manufacture. The manufacturing method of recycled PVC in this application may be a method of recycling PVC from waste materials.

The present application, as recycled from waste materials, has physical properties equivalent to those of PVC materials before use, while unnecessary impurities such as heavy metals are effectively removed, and at the same time, beneficial additives remain, providing recycled PVC materials and a method for manufacturing the same. aims to

In addition, the present application aims to obtain the recycled PVC material through an economical, environmentally friendly process that consumes little energy.

Among the physical properties mentioned in this specification, when the measured temperature and/or pressure affect the physical properties, the corresponding physical properties refer to physical properties measured at room temperature and/or normal pressure, unless otherwise specified.

In this application, the term room temperature refers to a natural temperature that is not heated or cooled, and may mean, for example, any temperature in the range of about 10 ° C to 30 ° C, 25 ° C, or 23 ° C.

In the present application, the term normal pressure is a pressure when not particularly reduced or increased, and may mean a pressure environment of about 740 mmHg to 780 mmHg, such as normal atmospheric pressure.

Among the physical properties mentioned in this specification, when measured humidity affects the physical properties, unless otherwise specified, the physical properties refer to physical properties measured at natural humidity that is not specially adjusted in the measured temperature and pressure state. do.

This application is directed to a method for manufacturing recycled PVC or a material comprising the same. The manufacturing method, in one example, may be a method of recycling PVC from waste.

In this specification, the term recycled PVC is PVC contained in waste and may refer to PVC recycled through a recycling process. At this time, the regeneration process may be a regeneration process of the present application to be described later.

In the above, the type of waste containing PVC is not particularly limited. PVC is applied to the manufacture of various products including building materials such as windows and doors, automobile parts, electric wires, hoses, agricultural films used for house cultivation of vegetables and fruits, or construction sheets. Therefore, wastes such as discarded building materials such as discarded windows, discarded automobile parts, discarded wires, discarded hoses, and discarded agricultural or construction sheets contain PVC, and these wastes are all used as raw materials for the method. can be used In one example, the waste may be a closed window.

Wastes containing PVC have different types of other components other than PVC, depending on the product from which the waste is derived. can be recovered

The term recycled PVC material herein may refer to a material comprising the recycled PVC and other materials, which may also be referred to as a recycled PVC composition or a polymer material. Other materials included in the recycled PVC material may be materials derived from the waste.

The content of the recycled PVC in the recycled PVC material is about 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, or 85% by weight. % or more, and may also be less than about 100% by weight, less than about 95% by weight, or less than about 90% by weight. In one example, the remaining amount excluding various components that may be included in the material to be described later may be the content of the recycled PVC.

The content of the recycled PVC can be obtained through ¹ H NMR analysis. The analysis may be performed, for example, using a 400 MHz FT-NMR Spectrometer (model name: AVANCE III HD 400, manufacturer: Bruker Biospin) (measurement conditions: 400 MHz, solvent: THF (tetrahydrofuran) -D8).

Although not particularly limited, the recycled PVC in the material may be included in a particle state. Although not limited thereto, the polymer material may be in a powder form.

Reclaimed PVC particles in the recycled PVC material, that is, PVC particles regenerated in the manner described below may be in a non-cluster particle state or a primary particle state. The non-cluster particle state or primary particle state is a different concept from the so-called cluster particle state or secondary particle state, and means that it is not a particle state formed by aggregation of a plurality of particles.

This is a characteristic that appears in PVC particles recovered by the method of the present application, and is a characteristic that does not appear in PVC before use. That is, the synthesized PVC before use, as exemplarily shown in FIG. 2, a plurality of particles of approximately spherical shape are aggregated and exist in a cluster or secondary particle state by the thermodynamic law, but the PVC recovered by the method of the present application In the case of , as shown exemplarily in FIG. 1 , it exists in a single particle state.

The recycled PVC particles in the non-cluster particle state or primary particle state in the material may have an average particle diameter in the range of 50 μm to 300 μm. The average particle diameter is the median particle diameter, so-called D50 particle diameter. In another example, the average particle diameter is 60 μm or more, 70 μm or more, 80 μm or more, 90 μm or more, or 100 μm or more, or 290 μm or less, 280 μm or less, 270 μm or less, 260 μm or less, 250 μm or less, 240 μm It may be about 230 μm or less, 220 μm or less, 210 μm or less, or 200 μm or less.

The recycled PVC material may include the recycled PVC and other materials. The other material may be a material derived from waste, such as the recycled PVC, and in particular, it may be a material that can compensate for the disadvantages of PVC, such as being somewhat hard, brittle, and lacking in flexibility. have. That is, the reclaimed PVC material regenerated according to the regeneration method of the present application may be a material in which impurities such as heavy metals are selectively removed and beneficial substances remain. You can get it.

Accordingly, in one example, the recycled PVC material may exhibit a first peak in the range of 4 ppm to 5 ppm and a second peak in the range of 1 ppm to 1.6 ppm in the ¹ H NMR spectrum. The second peak may be identified within a range of about 1 ppm to 1.5 ppm or about 1 ppm to 1.4 ppm in another example. The ¹ H NMR spectrum can be obtained through the same ¹ H NMR analysis as for confirming the content of the recycled PVC described above. Therefore, the analysis can be performed, for example, using a 400 MHz FT-NMR Spectrometer (model name: AVANCE III HD 400, manufacturer: Bruker Biospin) (measurement condition: 400 MHz, solvent: THF (tetrahydrofuran) -D8 ).

The first peak appearing in the range of 4 ppm to 5 ppm in the ¹ H NMR spectrum is a peak derived from recycled PVC, and may be, for example, a peak derived from a hydrogen atom of a carbon atom bonded to chlorine in PVC. have. In addition, the second peak appearing in the range of 1 ppm to 1.5 ppm in the spectrum is a material included in the recycled PVC material, is a material other than the recycled PVC, and is a peak derived from a material that can compensate for the disadvantages of PVC. can be

3 is a ¹ H NMR analysis result for one example of the PVC material. Referring to the figure, a peak (①) (first peak) derived from recycled PVC and a peak (③) (second peak) derived from other materials are also observed. Specific examples of the other material are not particularly limited, and may be, for example, MMA (methyl methacrylate), PMMA (poly (methyl methacrylate)), and/or ABS resin. The peak (②) identified at 2 to 3 ppm in FIG. 3 is also a peak derived from recycled PVC.

In the ¹ H NMR spectrum of the recycled PVC material, the ratio (second peak/first peak) of the area (integral value) of the second peak to the area (integral value) of the first peak is within a range of about 0.01 to 0.5. There may be. Under this ratio, the material that derives the second peak can adequately compensate for the disadvantages of PVC to obtain a recycled PVC material having excellent physical properties.

In another example, the ratio may be 0.02 or more, 0.03 or more, 0.04 or more, 0.05 or more, 0.06 or more, 0.07 or more, or 0.08 or more, or 0.4 or less, 0.3 or less, 0.2 or less, 0.1 or less, or 0.09 or less.

A material exhibiting the above ¹ H-NMR spectrum can be provided by the regeneration method according to the present application.

The PVC material may further include heavy metals in an amount of 500 ppm or less. The method of the present application can provide a material with a minimized ratio of heavy metals. Examples of the heavy metal include lead, cadmium, and the like, but are not limited thereto. In another example, the ratio of the heavy metal is 450 ppm or less, 400 ppm or less, 350 ppm or less, 300 ppm or less, 250 ppm or less, 200 ppm or less, 150 ppm or less, 100 ppm or less, 50 ppm or less, 40 ppm or less, 30 ppm or less , less than or equal to 20 ppm or less than or equal to 10 ppm, and also greater than or equal to 0 ppm, greater than 0 ppm, greater than or equal to 1 ppm, greater than or equal to 2 ppm, greater than or equal to 3 ppm, greater than or equal to 4 ppm, greater than or equal to 5 ppm, greater than or equal to 6 ppm, greater than or equal to 7 ppm, greater than or equal to 8 ppm , 9 ppm or more, or 10 ppm or more. That is, the material may not contain the heavy metal or may contain the heavy metal in a minimum amount within the above content range.

The heavy metal content can be confirmed through inductively coupled plasma emission spectrometry (ICP-OES). The analysis can be performed, for example, by using a measuring device from Agilent (Agilent, 5110 Series) through a so-called waste process test method (acid decomposition method) (KS C IEC62321-4 standard).

The polymer material may also contain a good solvent (ketones such as cyclic ketones and/or tetrahydrofuran (THF)). The good solvent may be a good solvent for the PVC. Such a good solvent may exist in the material by applying the good solvent in a regeneration step described later. The content ratio of the good solvent may be, for example, about 1,000 ppm or less, and the ratio may be 10 ppm or more in another example. Specific types of the good solvent will be described later. The content of the good solvent in the polymer material can be obtained by a known gas chromatography (GC) analysis method.

The polymeric material may also contain non-solvents (such as alcohols and/or ketones). The non-solvent may be a non-solvent for the PVC. Such a non-solvent may exist in the material by applying the non-solvent in a regeneration process described later. The non-solvent content may be, for example, about 500 ppm or less, and the ratio may be 10 ppm or more in another example. Specific types of the non-solvent are as described above. The content of the non-solvent in the polymer material can be obtained by a known gas chromatography (GC) analysis method.

The polymeric material may also further comprise fatty acids or salts of said fatty acids. The fatty acid or salt thereof may be a by-product of the heavy metal removal process described above. A specific example of the fatty acid is not particularly limited, and may be, for example, oleic acid or stearic acid.

The polymeric material may also include chlorinated poly(ethylene) (CPE). This component may be present when the recycled PVC is derived from waste windows.

The polymeric material may also include a phthalate compound. These compounds are derived from materials commonly added to PVC as plasticizers. Specific examples of the phthalate compound include di-iso-butyl phthalate (DIBP), di-n-butyl phthalate (DBP), butyl benzyl phthalate (BBP), di- (ethylhexyl) phthalate (DEHP), and Di-n-butyl phthalate (DOP). -Octyl phthalate), DINP (Di-isononyl phthalate) and/or DIDP (Di-isodecyl phthalate), but not limited thereto. The ratio of the phthalate compound in the material may be about 500 ppm or less, 450 ppm or less, 400 ppm or less, 350 ppm or less, 300 ppm or less, 250 ppm or less, 200 ppm or less, 150 ppm or less, or 100 ppm or less. . Since the phthalate compound may not be present in the material, the content is greater than or equal to 0 ppm, greater than 0 ppm, greater than 1 ppm, greater than 2 ppm, greater than 3 ppm, greater than 4 ppm, greater than 5 ppm, greater than 6 ppm, greater than 7 ppm. , 8 ppm or more, 9 ppm or more, or 10 ppm or more. The content of the phthalate compound may be measured by GC-MS (Gas Chromatography Mass Spectrometry), for example, using Agilent's 7890B (GC) and 5977B (MS) instruments.

In one example, the recycled PVC material may include aluminum. This aluminum may be derived from a heavy metal scavenger applied during the manufacturing process (recycling process) of the recycled PVC material of the present application. Among various heavy metal removal agents that can be applied in the present application, poly aluminum chloride (PAC), which will be described later, can effectively remove heavy metals and the like while effectively remaining beneficial substances that cause the second peak in the material. Then, aluminum derived from the PAC remains in the material.

Therefore, aluminum included in the recycled PVC material may be derived from PAC, which is a heavy metal removal agent described below, and specifically, may be derived from PAC represented by Chemical Formula 1 below.

The aluminum content in the recycled PVC material of the present application may vary depending on the amount of the heavy metal removal agent applied in the recycling process, but is usually about 1000 ppm or less, 950 ppm or less, 900 ppm or less, 850 ppm or less, 800 ppm 750 ppm or less, 700 ppm or less, 650 ppm or less, 600 ppm or less, 550 ppm or less, 500 ppm or less, 450 ppm or less, 400 ppm or less, 350 ppm or less, 300 ppm or less, 250 ppm or less, or 200 ppm or less , or may be greater than 0 ppm, greater than 50 ppm, greater than 100 ppm, greater than 150 ppm, greater than 200 ppm, greater than 250 ppm, or greater than 300 ppm.

By using a heavy metal removal agent so that the aluminum of the above level remains, it is possible to provide a recycled PVC material with desired characteristics.

The aluminum content can be measured by acid decomposition of the sample with Microwave equipment (Preekem's TOPEX) and ICP-OES equipment (Agilent's Technologies 5110). Details of the relevant measurement methods are summarized in the Examples section.

The polymer material may also include components such as charcoal (CaCO ₃ ) and TiO ₂ . These components may be mainly included in the material applied to the regeneration when the material is a waste window and when the material is not subjected to the filtering process. Since these materials are components necessary for the manufacture of windows and doors, the polymer material containing them can be applied to the manufacture of windows and doors. The content of components such as carbon (CaCO ₃ ) and TiO ₂ is not particularly limited, and is, for example, 10 wt% or less, 9 wt% or less, 8 wt% or less, 7 wt% or less, 6 wt% or less, or It may contain less than 5% by weight. The ratio may be about 0.1% by weight or more or about 1% by weight or more in another example.

The content of charcoal or the like can be confirmed by thermogravimetric analysis (TGA). The analysis can be performed, for example, using a TGA/DSC 3+ instrument from Mettler Toledo, and the temperature range from 30 °C to 1,000 °C under a nitrogen (N ₂ ) atmosphere at a heating rate of 10 °C/min. It can be done by heating it up.

The content of charcoal or the like can also be confirmed through the above-mentioned inductively coupled plasma emission spectrometry (ICP-OES). This analysis can be performed, for example, using Agilent's 5110 Series, and can be performed through a so-called waste process test method (acid decomposition method) (KS C IEC62321-4 standard).

The recycled PVC material may exhibit color properties equivalent to PVC before use.

For example, the recycled PVC material may have a b value of 6.5 or less in CIE Lab color coordinates. In another example, the b value is 6.4 or less, 6.3 or less, 6.2 or less, 6.1 or less, 6.0 or less, 5.9 or less, 5.8 or less, 5.7 or less, 5.6 or less, 5.5 or less, 5.4 or less, 5.3 or less, 5.2 or less, 5.1 or less, 5 4.9 or less, 4.8 or less, 4.7 or less, 4.6 or less, 4.5 or less, 4.4 or less, 4.3 or less, 4.2 or less, 4.1 or less, 4 or less, 3.9 or less, 3.8 or less, 3.7 or less, or 3.6 or less, or 1 or more, 1.1 or more , 1.2+, 1.3+, 1.4+, 1.5+, 1.6+, 1.7+, 1.8+, 1.9+, 2+, 2.1+, 2.2+, 2.3+, 2.4+, 2.5+, 2.6+, 2.7+, 2.8 3 or more, 2.9 or more, 3 or more, 3.1 or more, 3.2 or more, 3.3 or more, 3.4 or more, 3.5 or more, 3.6 or more, 3.7 or more, 3.8 or more, 3.9 or more, 4.0 or more, 4.1 or more, 4.2 or more, 4.3 or more, 4.4 or more, It may be about 4.5 or more, 4.6 or more, 4.7 or more, 4.8 or more, 4.9 or more, 5.0 or more, 5.1 or more, 5.2 or more, 5.3 or more, or 5.4 or more.

The polymer material may have an L value in the range of 70 to 100 in CIE Lab color coordinates. In another example, the L value is 72 or more, 74 or more, 76 or more, 78 or more, 80 or more, 82 or more, 84 or more, 86 or more, 88 or more, 90 or more, or 92 or more, 98 or less, 96 or less, 94 or less, or It may be around 93 or less.

The polymer material may have an a value of 5 or less in CIE Lab color coordinates. In another example, the a value is 4.9 or less, 4.8 or less, 4.7 or less, 4.6 or less, 4.5 or less, 4.4 or less, 4.3 or less, 4.2 or less, 4.1 or less, 4.0 or less, 3.9 or less, 3.8 or less, 3.7 or less, 3.6 or less, 3.5 3.4 or less, 3.3 or less, 3.2 or less, 3.1 or less, 3.0 or less, 2.9 or less, 2.8 or less, 2.7 or less, 2.6 or less, 2.5 or less, 2.4 or less, 2.3 or less, 2.2 or less, 2.1 or less, 2.0 or less, 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, 1.1 or less, 1.0 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.3 or less, 0.2 or less , less than 0.1 or less than 0.0, or greater than -2, greater than -1.8, greater than -1.6, greater than -1.4, greater than -1.2, greater than -1.0, greater than -0.8, greater than -0.6, greater than -0.4, greater than -0.2, greater than 0.0 , may be about 0.5 or more, 1 or more, or 1.5 or more.

The recycled PVC material may also satisfy the following relational expression 1.

[Relationship 1]

(a ² + b ² ) ^1/2 ≤ 6

In relational expression 1, a and b are a and b values of the CIE Lab color coordinates of the recycled PVC material, respectively.

In the above relational expression 1, (a ² +b ² ) ^1/2 is 5.9 or less, 5.8 or less, 5.7 or less, 5.6 or less, 5.5 or less, 5.4 or less, 5.3 or less, 5.2 or less, 5.1 or less, 5.0 or less, or 4.9 or less in another example. , 4.8 or less, 4.7 or less, 4.6 or less, 4.5 or less, 4.4 or less, 4.3 or less, 4.2 or less, 4.1 or less, 4.0 or less, 3.9 or less, 3.8 or less, 3.7 or less, 3.6 or less, 3.5 or less, 3.4 or less, 3.3 or less, 3.2 1 or more, 1.1 or more, 1.2 or more, 1.3 or more, 1.4 or more, 1.5 or more, 1.6 or more, 1.7 or more, 1.8 or more, 1.9 or more, 2 or more, 2.1 or more, 2.2 or more, 2.3+, 2.4+, 2.5+, 2.6+, 2.7+, 2.8+, 2.9+, 3+, 3.1+, 3.2+, 3.3+, 3.4+, 3.5+, 3.6+, 3.7+, 3.8+, 3.9+ , 4+, 4.1+, 4.2+, 4.3+, 4.4+, 4.5+, 4.6+, 4.7+, 4.8+, 4.9+, 5+, 5.1+, 5.2+, 5.3+, 5.4+, 5.5+, 5.6 or higher, 5.7 or higher, 5.8 or higher, or 5.9 or higher.

Satisfaction of the b value, L value, a value, and/or relational expression 1 means that the color characteristics of the recycled PVC are close to those of PVC before use, and the characteristics of PVC that can be easily colored in various colors are maintained.

These excellent color properties are inherent in the recycled PVC obtained by the method according to the present application.

That is, according to the regeneration method of the present invention, it is possible to remove impurities such as heavy metals and leave useful components while minimizing damage to PVC during the regeneration process. When a lot of damage is applied to PVC during the regeneration process of PVC, a relatively large number of double bonds are generated in the material, and these double bonds affect the color characteristics of the material. According to the method of the present application, it is possible to minimize defects such as the double bond generated in the regeneration process, and thus maintain excellent color characteristics of the material as described above.

This application also relates to a method for manufacturing recycled PVC material, which manufacturing method may be a method for recycling recycled PVC material from waste.

Recycled PVC material with excellent properties can be obtained by the method of the present application described later.

The method for producing recycled PVC of the present application may include mixing waste containing PVC and a treatment agent. The treatment agent may include a good solvent for the PVC.

The types of waste containing PVC are as described above.

Although not limited thereto, it may be advantageous to use waste of the same type of product as the product to be manufactured using recycled PVC as the waste. For example, if recycled PVC is to be applied to the manufacture of windows and doors, discarded windows and doors can be used as the waste.

The treatment agent mixed with the waste containing PVC may be a good solvent for the PVC or may contain the good solvent. Therefore, preparing the mixture may be a step of obtaining a mixture containing PVC dissolved in the good solvent.

When the treatment agent contains a good solvent, the ratio of the good solvent in the treatment agent can be adjusted to an appropriate range. For example, the treatment agent contains the good solvent in an amount of 50 vol% or more, 55 vol% or more, 60 vol% or more, 65 vol% or more, 70 vol% or more, 75 vol% or more, 80 vol% or more, 85 vol% or more, 90 vol% or more, or 95 vol% or more. In one example, the treatment agent may include only the good solvent. Therefore, the upper limit of the proportion of the good solvent in the treatment agent is 100% by volume.

In the present application, as the good solvent, a ketone or THF (Tetrahydrofuran) may be applied. Therefore, the ratio of the ketone or THF (tetrahydrofuran) in the treatment agent is 50 vol% or more, 55 vol% or more, 60 vol% or more, 65 vol% or more, 70 vol% or more, 75 vol% or more, 80 vol% or more, 85 vol% or more, 90 vol% or more, or 95 vol% or more, and the upper limit thereof may be 100 vol%.

There is no particular limitation on the type of ketone that can be applied as a good solvent, for example, 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms, such as methyl ethyl ketone. A release ketone or a cyclic ketone can be used.

In particular, by applying a cyclic ketone as a good solvent, the regeneration process can be performed at a relatively low temperature. In addition, as will be described later, the cyclic ketone can be easily recovered and reused even when a non-solvent is applied in the recovery process of PVC through the application of the cyclic ketone. Therefore, through the application of the good solvent, the regeneration process can be economical and low energy consumption process. In addition, the selection of the good solvent enables other processes of the present application (eg, a phase separation process to be described later) to proceed, or to obtain recycled PVC in a state in which impurities are better removed in conjunction with the other processes make it possible

In one example, the cyclic ketone may have a molar mass in the range of 70 to 150 g/mol. In another example, the molar mass is 80 g/mol or more, 90 g/mol or more, or 95 g/mol or more, or 140 g/mol or less, 130 g/mol or less, 120 g/mol or less, 110 g/mol or less, or 100 g/mol or less. It may be on the order of g/mol or less.

The boiling point of the cyclic ketone may be in the range of 130°C to 200°C. In another example, the boiling point is 135 ° C or higher, 140 ° C or higher, 145 ° C or higher or 150 ° C or higher, or 195 ° C or lower, 190 ° C or lower, 185 ° C or lower, 180 ° C or lower, 175 ° C or lower, 170 ° C or lower, 165 ° C or lower. Alternatively, it may be about 160° C. or less.

The cyclic ketone may have a water solubility of 15 g/100 mL or less at 20°C. In another example, the water solubility is 13 g/100 mL or less, 11 g/100 mL or less, or 9 g/100 mL or less, or 1 g/100 mL or more, 2 g/100 mL or more, 3 g/100 mL or more, 4 g/100 mL or more, or 5 g/100 mL. Or more, 6 g/100 mL or more, 7 g/100 mL or more, or 8 g/100 mL or more.

The cyclic ketone may have a vapor pressure in the range of 1 to 10 mmHg at 20 °C. The vapor pressure may be 2 mmHg or more, 3 mmHg or more, or 4 mmHg or more, or 9 mmHg or less, 8 mmHg or less, 7 mmHg or less, or 6 mmHg or less in another example.

As the cyclic ketone, one that satisfies the above characteristics may be appropriately selected and used, and specific examples thereof are not particularly limited. For example, as the cyclic ketone, a compound having 3 to 10, 5 to 9, or 5 to 8 carbon atoms forming a ring structure may be used, and for example, cyclohexanone may be used. , but is not limited thereto.

Through the selection of the good solvent, the mixing process of the treatment agent and the waste can be performed at a low temperature. That is, through the selection of the above-described good solvent, an efficient PVC dissolution process can be performed even at a relatively low temperature, and subsequent processes can also be effectively performed. In one example, the mixing process with the good solvent may proceed at a temperature range of about 10 °C to 100 °C. The temperature range is, in another example, 12 ° C or more, 14 ° C or more, 16 ° C or more, 18 ° C or more or 20 ° C or more, or 95 ° C or less, 90 ° C or less, 85 ° C or less, 80 ° C or less, 75 ° C or less, 70 ° C. It may be 65°C or less, 60°C or less, 55°C or less, 50°C or less, 45°C or less, 40°C or less, 35°C or less, or 30°C or less.

The kind of the above-described good solvent is the same as the good solvent included in the above-described PVC material.

The amount of the good solvent used in the mixing process is not particularly limited, but for efficient process progress, for example, 100 to 5,000 parts by weight of the good solvent may be mixed with respect to 100 parts by weight of the PVC-containing waste. Therefore, the treatment agent is used in an amount such that the ratio of the good solvent to the waste falls within the above range. Within this range, PVC can be effectively dissolved in a good solvent, and subsequent processes (eg, a heavy metal removal process, a phase separation process, etc.) can also be effectively performed. In another example, the mixing ratio of the good solvent is 200 parts by weight or more, 300 parts by weight or more, 400 parts by weight or more, 500 parts by weight or more, 600 parts by weight or more, 700 parts by weight or more, 800 parts by weight or more, 900 parts by weight or more, 1,000 parts by weight or more, 1,500 parts by weight or more, 4,500 parts by weight or less, 4,000 parts by weight or less, 3,500 parts by weight or less, 3000 parts by weight or less, 2500 parts by weight or less, 2000 parts by weight or less, or 1500 parts by weight or less.

Following the mixing process, a PVC recovery step may proceed. This recovering step may, in one example, include inducing phase separation of the mixture; and separating a phase including PVC from the phase-separated mixture.

Therefore, the manufacturing method of the recycled PVC may further include inducing phase separation in the mixture of the waste and the good solvent.

The step of inducing phase separation may be performed to obtain a recycled PVC material from which impurities are more efficiently removed. Waste, which is a raw material for obtaining recycled PVC, contains various impurities, and some of these impurities (eg, heavy metals, etc.) exist in a phase different from PVC in a phase-separated mixture. Therefore, after inducing phase separation in the mixture, only the phase containing PVC is separated from the separated phases, and PVC is recovered, thereby obtaining a recycled PVC material in which impurities are more effectively removed and useful substances remain.

A method of inducing phase separation in the mixture is not particularly limited. In one example, the method of inducing the phase separation may be a step of mixing the mixture and an aqueous solvent. There is no particular limitation on the type of aqueous solvent, and water may be used, for example. The treatment agent used in the preparation of the mixture contains a cyclic ketone or the like as a good solvent, and the cyclic ketone is a substance capable of phase separation from the aqueous solvent. Therefore, the phase separation may be induced by mixing the mixture and the aqueous solvent.

These aqueous solvents may be mixed with the mixture alone or with other components at appropriate points in the course of the process. For example, if a process of applying a heavy metal scavenger or a non-solvent to be described later is performed in the process of the present application, an aqueous solvent may be added to the mixture together with the heavy metal scavenger and/or the non-solvent. The aqueous solvent may be added only once during the process or divided into several times.

The amount of the aqueous solvent (eg water) is not particularly limited as long as it is selected so as to induce an appropriate phase separation. In general, the aqueous solvent may be applied so that the volume ratio (volume of aqueous solvent/volume of good solvent) of the aqueous solvent and the good solvent (cyclic ketone, etc.) in the treatment agent is in the range of 0.1 to 10. The volume ratio (aqueous solvent volume / good solvent volume) is, in another example, 0.2 or more, 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, or 1 or more, 9 or less, 8 or less, It may be about 7 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

In another example, the aqueous solvent may be mixed so that about 100 to 3,000 good solvents are present relative to 100 parts by weight of the aqueous solvent. The ratio is 150 parts by weight or more, 200 parts by weight or more, 250 parts by weight or more, 300 parts by weight or more, 350 parts by weight or more, 400 parts by weight or more, 450 parts by weight or more, 500 parts by weight or more, based on 100 parts by weight of the aqueous solvent. About 550 parts by weight or more, 600 parts by weight or more, 650 parts by weight or more, 700 parts by weight or more, 750 parts by weight or more, 800 parts by weight or more, 850 parts by weight or more, 900 parts by weight or more, 950 parts by weight or more, or 1000 parts by weight or more Or, 2800 parts by weight or less, 2600 parts by weight or less, 2400 parts by weight or less, 2200 parts by weight or less, 2000 parts by weight or less, 1800 parts by weight or less, 1600 parts by weight or less, 1400 parts by weight or less, 1200 parts by weight or less, 1100 parts by weight It may be less than or about 1000 parts by weight or less.

When the aqueous solvent is added alone or used in a mixed state with a heavy metal remover and/or non-solvent, the amount of the aqueous solvent may be adjusted to be within the above range. When the amount of the aqueous solvent applied together with the heavy metal remover and/or the non-solvent is insufficient to induce phase separation, the aqueous solvent may be additionally added separately.

The phase separation induction process can also be performed at a low temperature. For example, the phase separation induction process may proceed at a temperature range of about 10 °C to 50 °C. In another example, the temperature range may be 12 ° C or higher, 14 ° C or higher, 16 ° C or higher, 18 ° C or higher or 20 ° C or higher, or 45 ° C or lower, 40 ° C or lower, 35 ° C or lower, or 30 ° C or lower.

Following the phase separation step, a step of separating a phase including PVC from the phase separated mixture may be performed. When phase separation is induced by introducing an aqueous component, the mixture is separated into an organic phase and an aqueous phase, and PVC usually exists in the organic phase including cyclic ketones and the like. Accordingly, the organic phase may be separated from the phase-separated mixture following the above step. Of course, if PVC is present in the aqueous phase, it will separate the aqueous phase.

After separation of the PVC-containing phase, further processing to recover the PVC may be carried out if necessary.

For example, the additional process may be a process of drying the PVC-containing phase. Through the drying, PVC in the organic component may be recovered. This drying process may be carried out at a temperature range of about 20 °C to 90 °C or 40 °C to 70 °C, for example. In the present application, an efficient drying process can be performed within the above range through the use of the specific good solvent described above, thereby effectively regenerating PVC while minimizing or eliminating the damage caused to PVC by high temperature.

There is no particular limitation on the duration of the drying process, and the desired PVC can be recovered by maintaining the temperature under the temperature for an appropriate time according to the purpose.

In another example, the additional process may be a process of mixing the PVC-containing phase with a poor solvent for the PVC. In addition, the mixing process with the non-solvent may be a mixing process of the PVC-containing phase and the non-solvent, but when the phase separation process is not performed, the mixing process is performed with the waste and the treatment agent (good solvent or good solvent). It may be a process of mixing a mixture of a treatment agent containing) and the non-solvent.

Accordingly, the method for producing the recycled PVC may further include mixing the PVC-containing phase and the non-solvent or mixing the mixture of the waste and treatment agent with the non-solvent.

Through mixing with a non-solvent, the PVC can be precipitated in an organic component or mixture, and the PVC can be recovered, and through this process, recycled PVC of higher purity can be obtained.

The type of non-solvent is not particularly limited, but, for example, alcohol, water, or hexane may be used as the non-solvent. Although not particularly limited, a monohydric alcohol having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms (eg, methanol, ethanol, propanol, etc.) is the non-solvent can be used as

In one example, as a non-solvent, the absolute value of the difference in boiling point from the cyclic ketone is 40 ° C or more, 45 ° C or more, 50 ° C or more, 55 ° C or more, 60 ° C or more, 65 ° C or more, 70 ° C or more, A non-solvent above 75°C, above 80°C or above 85°C may be applied. As the non-solvent, one having a boiling point lower than that of the cyclic ketone while the absolute value of the difference in boiling point from the cyclic ketone is within the above range may be used. This non-solvent enables more efficient precipitation of PVC. In addition, in the case of having the above boiling point difference, only the cyclic ketone or non-solvent can be effectively recovered from the mixture of the cyclic ketone and the non-solvent, and by reusing the recovered cyclic ketone or non-solvent in the process, it is more economical and , it is possible to proceed with a process of low energy consumption. In the above, there is no particular limitation on the upper limit of the absolute value of the difference between the boiling points of the cyclic ketone and the non-solvent, and for example, the absolute value of the difference in boiling points is 200 ° C. or less, 180 ° C. °C or less, 120 °C or less, 100 °C or less, or 95 °C or less.

The kind of non-solvent described above is the same as the good solvent contained in the above-described PVC material.

The amount of the non-solvent to be mixed is not particularly limited as long as suitable PVC can be precipitated. For example, the non-solvent may be mixed in an amount of about 50 to 1000 parts by weight based on 100 parts by weight of the PVC-containing phase. In another example, the ratio is 100 parts by weight or more, 150 parts by weight or more, or 200 parts by weight or more, or 900 parts by weight or less, 800 parts by weight or less, 700 parts by weight or less, 600 parts by weight or less, 500 parts by weight or less, 400 parts by weight or less. It may be less than or about 300 parts by weight or less.

The non-solvent may be mixed with the PVC-containing phase by itself or mixed with the organic component in a state of being mixed with other components. For example, as described above, the non-solvent (e.g., alcohol) can be mixed with the PVC-containing phase in a mixed state with an aqueous solvent (e.g., water), whereby the PVC is also efficient. precipitation may be possible. In this case, when the phase containing PVC is an organic phase, an additional phase separation effect can be obtained by the mixing, and a desired recycled PVC can be obtained more effectively by this effect.

When a mixture of a non-solvent and an aqueous solvent is mixed, the ratio of the non-solvent in the mixture may be adjusted to enable efficient precipitation of PVC. For example, the non-solvent in the mixture is about 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, 45% or more, 50% or more, 55% or more by weight. % or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, 90% or more or 95% or more. There is no upper limit on the content of the non-solvent in the mixture. That is, since the non-solvent can be applied even without being mixed with the aqueous solvent as described above, the content of the non-solvent in the mixture may be, for example, less than 100% by weight.

The process of mixing the non-solvent with the PVC-containing phase may also be performed at a relatively low temperature. For example, the process of mixing the non-solvent with the PVC-containing phase may be performed at a temperature range of about 10 °C to 50 °C. In another example, the temperature range may be 12 ° C or higher, 14 ° C or higher, 16 ° C or higher, 18 ° C or higher or 20 ° C or higher, or 45 ° C or lower, 40 ° C or lower, 35 ° C or lower, or 30 ° C or lower.

Recycled PVC can be obtained by recovering PVC precipitated by mixing with the non-solvent by an appropriate means. An additional drying process may be performed on such recycled PVC.

In the manufacturing method of the present application, other processes may be further performed in addition to those described above.

For example, the manufacturing method may further include a step of removing heavy metals from the mixture of the waste and treatment agent, and the step may be a process of mixing the mixture with a heavy metal removing agent. If the mixing process with such a heavy metal remover proceeds, heavy metals can be effectively removed from waste. The mixing process with the heavy metal removing agent may be performed at an appropriate time in the process of the present application, for example, before the phase separation induction process. In another example, when the heavy metal scavenger is added together with the aqueous solvent as described above, the phase separation induction process and the process of adding the heavy metal scavenger are performed simultaneously.

Waste used as a raw material in the production of recycled PVC of the present application may include heavy metals. Heavy metals, as is well known, refer to metals having a relatively high density, atomic weight or large atomic number, among which cadmium or lead is harmful to the human body. Therefore, it is required to remove the harmful heavy metals from recycled PVC as much as possible. Through the step of adding the heavy metal remover, the heavy metal can be removed more efficiently.

As the heavy metal removing agent, for example, an acid, a salt and/or a base may be used, or a solution (eg aqueous solution) containing the above components may be used. In the above, as the salt, various inorganic salts (including polyvalent inorganic salts) such as NaCl, poly aluminum chloride (PAC), liquid, iron chloride, aluminum sulfate, magnesium sulfate, and/or acid clay may be used. And, as the base, NaOH or KOH may be used, but is not limited thereto. In addition, various organic or inorganic acids are included in the category of acid that can be used as the heavy metal removal agent, and examples thereof include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, acetic acid, and/or citric acid. In terms of effectively removing heavy metals without damaging the properties of PVC, acid, NaCl and / or poly aluminum chloride (PAC) or a solution containing the same (eg, aqueous solution) may be used as the heavy metal removal agent, , in particular PAC or a solution containing the same (eg aqueous solution) can be used.

As the PAC, a known PAC may be used without particular limitation. Typically, PAC has a structure represented by Formula 1 below.

[Formula 1]

[Al ₂ (OH) _n Cl _6-n ] _m

In Formula 1, n is a number in the range of 1 to 5, and m is a number of 10 or less.

In Formula 1, n may be 2 or more, 3 or more, 4 or more, or 4.5 or more, or 4 or less, 3 or less, 2 or less, or 1.5 or less in another example.

In Formula 1, m is, in another example, 0 or more, more than 0, 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, or 9 or more, 9 or less, 8 or less, It may be 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, or 1 or less.

Among the acids, for example, those having a pKa in the range of about -10 to 5 can be used. In another example, the pKa of the applicable acid is -9 or more, -8 or more, or -7 or more, or 4 or less, 3 or less, 2 or less, 1 or less, 0 or less, -1 or less, -2 or less, -3 or less, It can be -4 or less or -5 or less. Hydrochloric acid may be exemplified as an acid having such a pKa, but the type of applicable acid is not limited thereto.

The heavy metal remover may be mixed with the mixture alone as described above, or may be mixed with the mixture in an aqueous solution. When mixed in an aqueous solution state, the mixing may contribute to the phase separation process as described above.

When the heavy metal scavenger is used in an aqueous solution, the ratio of the heavy metal scavenger in the aqueous solution is not particularly limited. For example, in this case, the ratio of the heavy metal scavenger may be adjusted in consideration of the ratio per 1 mole of heavy metal and the phase separation efficiency described below. For example, when the heavy metal scavenger is the PAC, the ratio in the aqueous solution may be about 5 to 50% by weight. In another example, the ratio is 7% by weight or more, 9% by weight or more, 11% by weight or more, 13% by weight or more, or 15% by weight or more, or 45% by weight or less, 40% by weight or less, 35% by weight or less, 30% by weight or less. It may be less than or about 25% by weight or less.

In addition, when the heavy metal remover is an acid, the acid aqueous solution may be prepared to have a molar concentration (M) of about 0.1 to about 10. In another example, the molar concentration (M) may be 0.3 or more, 0.5 or more, 0.7 or more, or 0.8 or more, or 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, or 2 or less.

The amount of the heavy metal remover applied during the mixing is not particularly limited. For example, a heavy metal remover within a range of 0.1 to 50 mol per 1 mol of the heavy metal may be mixed in consideration of the heavy metal content present in the waste. Theoretically, 1 mole of heavy metal contained in waste can be removed by reacting with 1 to 2 moles of heavy metal removal agent, but in practice, the amount of heavy metal removal agent applied according to the solubility of heavy metal removes heavy metal present in waste Even if it is possible, the amount of heavy metals actually removed may be insignificant. However, according to the method of the present application, it is possible to effectively remove heavy metals contained in the waste even in a low-temperature process through the selection of an appropriate good solvent through a relatively small amount of the heavy metal remover, and accordingly, the heavy metal is effectively removed while the heavy metal remover It is possible to obtain recycled PVC without deterioration of physical properties due to the use of

In other examples, the ratio is 0.3 mol or more, 0.5 mol or more, 0.7 mol or more, 0.9 mol or more, 45 mol or less, 40 mol or less, 35 mol or less, 30 mol or less, 25 mol or less, 20 mol or less per 1 mol of heavy metal. , 15 moles or less, 10 moles or less, 8 moles or less, 6 moles or less, or 4 moles or less.

For example, in the present application, when an acid is used as the heavy metal removal agent and applied in an aqueous solution, heavy metal removal is possible even in a low acidic aqueous solution, and the heavy metal remover is reduced through the use of a low acidic aqueous solution. Possible adverse effects on recycled PVC can also be minimized. For example, in the method of the present application, as the acidic aqueous solution, an aqueous solution having a molar concentration (M) of about 0.1 to about 5 may be used. The molar concentration (M) may be 0.3 or more, 0.5 or more, 0.7 or more, or 0.8 or more, or 4 or less, 3 or less, or 2 or less in another example. Even when such a low-acid aqueous solution is used as a heavy metal remover, the mixing amount may be such that the heavy metal remover (acid) is mixed in the range of 0.1 to 50 moles per 1 mole of heavy metal contained in the waste. have. More specific details of the range are as described above.

In another example, in the present application, the heavy metal remover may be mixed so that the good solvent is present in a weight ratio of about 1 to 2,000 parts by weight in a mixture containing PVC and a good solvent mixed with 100 parts by weight of the heavy metal remover. In another example, the ratio of the good solvent is 3 parts by weight or more, 5 parts by weight or more, 7 parts by weight or more, 9 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 25 parts by weight or more. 50 parts by weight or more, 100 parts by weight or more, 150 parts by weight or more, 200 parts by weight or more, 250 parts by weight or more, 300 parts by weight or more, 350 parts by weight or more, 400 parts by weight or more, 450 parts by weight or more, 500 parts by weight 550 parts by weight or more, 600 parts by weight or more, 650 parts by weight or more, 700 parts by weight or more, 750 parts by weight or more, 800 parts by weight or more, 850 parts by weight or more, 900 parts by weight or more, 950 parts by weight or more, 1000 parts by weight or about 1500 parts by weight or more, 1500 parts by weight or less, 1000 parts by weight or less, 950 parts by weight or less, 900 parts by weight or less, 850 parts by weight or less, 800 parts by weight or less, 750 parts by weight or less, 700 parts by weight or less, 650 600 parts by weight or less, 550 parts by weight or less, 500 parts by weight or less, 450 parts by weight or less, 400 parts by weight or less, 350 parts by weight or less, 300 parts by weight or less, 250 parts by weight or less, 200 parts by weight or less, 150 100 parts by weight or less, 90 parts by weight or less, 80 parts by weight or less, 70 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, or 10 It may be on the order of parts by weight or less.

Under these ratios, recycled PVC material with desired properties can be efficiently recovered. In particular, the ratio may be appropriate when the heavy metal scavenger is or is an aqueous solution containing the acid, NaCl and/or PAC.

In the present application, the heavy metal removal process can also be performed at a low temperature, and since heavy metals can be efficiently removed even under such a low temperature process, energy consumption is reduced, and damage to recycled PVC that can be applied under a high temperature process is also reduced. It can be prevented.

For example, the heavy metal removal process, that is, the mixing process of the mixture of the waste and the good solvent and the heavy metal removal agent may be performed at a temperature range of about 10°C to 50°C. In another example, the temperature range may be 12 ° C or higher, 14 ° C or higher, 16 ° C or higher, 18 ° C or higher or 20 ° C or higher, or 45 ° C or lower, 40 ° C or lower, 35 ° C or lower, or 30 ° C or lower.

The manufacturing process of the present application may also additionally perform a crushing process of the waste. This pulverization process is any process that can be performed using an appropriate pulverization means, and when the pulverization process is performed, the dissolution efficiency of the waste into the treatment agent can be further increased. The point at which the crushing process is performed is not particularly limited, and if it is performed, it may be performed before the mixing process of the waste and the treatment agent. At this time, the grinding method is not particularly limited, and a known grinding method may be applied.

The manufacturing process of the present application may perform a filtering process if necessary. For example, a filtering process may be performed on a mixture including at least two components selected from the group consisting of the waste, treatment agent, aqueous solvent, heavy metal remover, and non-solvent. This filtering process is an arbitrary process, and if performed, it may be performed, for example, before or after the phase separation induction process, before or after the heavy metal remover input process, and/or before or after the non-solvent input process. . In one example, the filtering process is performed, for example, for a mixture of at least the waste and a good solvent or a mixture of a treatment agent containing the good solvent and a non-solvent, or a mixture of a PVC-containing phase and a non-solvent recovered after phase separation. can be performed

In one example, if the step of adding the heavy metal remover is performed, the filtering step may be performed between the mixing step of the treatment agent and the waste and the mixing step of the heavy metal remover. In this case, the mixture of treatment agent and waste may be mixed with the heavy metal removal agent again after once subjected to a filtering process.

Components that need to be removed among the components present in the mixture of the treatment agent and the waste may be first filtered out by the filtering process.

The method of performing the filtering process is not particularly limited, and, for example, the filtering process may be performed by filtering the mixture with an appropriate filter medium.

There is no particular limitation on the filter medium that can be applied in this process, and for example, the filtering is performed using an appropriate mesh, or a filter medium such as magnesium sulfate, aluminum sulfate, silica, celite, or activated carbon is used. Filtering can be exemplified. Also, filtering may be performed by combining two or more of the above-mentioned means.

Additional components may be applied in the filtering process. For example, additional components may be used in the filtering process. For example, in the filtering process, components such as dichloromethane (DCM), tetrahydrofuran (THF), dichloroethane (DCE), methyl ethyl ketone (MEK), or dimethyl sulfoxide (DMSO) pass through the filter medium together with the mixture to be filtered. can These components can prevent the filter medium from deteriorating or the filtering performance of the filter medium from deteriorating during the filtering process. For example, an effective filtering process may be performed by passing these components through the filter medium in a state in which an appropriate amount of these components are mixed with the mixture. The proportions of the components mixed in this process are adjusted according to the purpose and are not particularly limited. For example, components such as dichloromethane (DCM) or tetrahydrofuran (THF) may be used in an amount of about 0.5 to 20 parts by weight or about 5 to 10 parts by weight based on 100 parts by weight of the mixture to be filtered.

The mixture may also be treated with MgSO ₄ . Heavy metals can be removed more efficiently by such a treatment. The treatment with MgSO ₄ may be performed together with the filtering process (eg, a method of including the MgSO ₄ in a filter medium in the filtering process), or may be performed independently before or after the filtering. Alternatively, the filtering process may not be performed, and only the treatment with MgSO ₄ may be performed. The treatment method with the MgSO ₄ is not particularly limited, and for example, the treatment may be carried out by removing the MgSO ₄ in a known manner after appropriately contacting the MgSO ₄ and the mixture by mixing or the like. have.

In the present application, the filtering process and/or the treatment with MgSO ₄ can also be performed at a relatively low temperature. For example, the process or treatment may proceed at a temperature range of about 10 °C to 50 °C. In another example, the temperature range may be 12 ° C or higher, 14 ° C or higher, 16 ° C or higher, 18 ° C or higher or 20 ° C or higher, or 45 ° C or lower, 40 ° C or lower, 35 ° C or lower or 30 ° C or lower.

In the manufacturing method of the present application, if necessary, known additional treatment (eg, washing, drying, dehydration, etc.) may be performed on the recovered PVC.

In one example, all processes of the method for manufacturing recycled PVC (except for the drying process if the above-described drying process for recovery of PVC is performed) may be performed at a relatively low temperature.

For example, all processes of the method for manufacturing recycled PVC (except for the process when the drying process is performed) may be performed at a temperature range of about 10° C. to 50° C. In another example, the temperature range may be 12 ° C or higher, 14 ° C or higher, 16 ° C or higher, 18 ° C or higher or 20 ° C or higher, or 45 ° C or lower, 40 ° C or lower, 35 ° C or lower, or 30 ° C or lower.

In the method of the present application, PVC with excellent physical properties can be effectively recovered even under the relatively low temperature, and the damage that may be applied to PVC during the process is minimized by the process being performed as a low-temperature process, and the required energy consumption can be minimized.

This application also relates to a resin molded body comprising the above-described recycled PVC material or a material recycled by the above manufacturing method. The type of the resin molded body is not particularly limited, and may be, for example, a window or door. A method for producing the resin molded body using the polymer material is not particularly limited, and a known method may be applied, and the PVC particles in the resin molded body may be in a particle state or not.

The resin molded body may have a b value in the range of 3 to 6 in CIE Lab color coordinates. In another example, the b value may be 3.1 or more, 3.2 or more, 3.3 or more, 3.4 or more, 3.5 or more, 3.6 or more, or 3.7 or more, or 5.5 or less, 5 or less, 4.5 or less, or 4 or less.

The resin molded body may have an L value in the range of 80 to 100 in CIE Lab color coordinates. In another example, the L value may be 82 or more, 84 or more, 86 or more, 88 or more, 90 or more, or 92 or more, or 98 or less, 96 or less, 94 or less, or 93 or less.

The resin molded body may have an a value in the range of 0 to 5 in CIE Lab color coordinates. In another example, the a value may be 0.2 or more, 0.4 or more, 0.6 or more, or 0.8 or more, or 4 or less, 3 or less, 2 or less, or 1 or less.

The resin molded body (eg, window or door) may have a tensile yield strength of 36 MN/m ² or more. The strength may be, for example, 38 MN/m ² or more, 40 MN/m ² or more, or 60 MN/m ² or less.

The resin molded body (eg, window or door) may have a tensile elongation at break of 100% or more. The elongation may be, for example, 120% or more, 140% or more, 160% or more, or 250% or less.

The resin molded body (eg, window or door) may have a Charpy impact value (-10°C) of 4.9 KJ/m ² or more. The Charpy impact value may be, for example, 6 KJ/m ² or more, 8 KJ/m ² or more, or 20 KJ/m ² or less.

The resin molded body (for example, a window or door) may also have a flexural modulus of 1960 MN/m ² or more.

The resin molded body (for example, a window or door) may also have a heat elasticity of 2.5% or less.

The resin molded body (for example, windows and doors) may also have a Vikat softening temperature of 83°C or higher. In another example, the temperature may be 85° C. or higher or 95° C. or lower.

The resin molded body (for example, a window or door) may also have a hardness (HRR) of 85 or more. The hardness may be 90 or more, 95 or more, or 100 or less in another example.

The resin molded body (for example, a window or door) may also have a heat/cold elasticity of about 0.2% or less. In another example, the elasticity may be 0.15% or less, 0.1% or less, or 0% or more.

The tensile yield strength, tensile elongation at break, Lyarpy impact value, flexural modulus, heating elasticity, Vikat softening temperature, hardness, heat and cold cycle elasticity, etc. may be obtained according to specifications.

This application is directed to recycled PVC materials and methods for their manufacture. The manufacturing method of recycled PVC in this application may be a method of recycling PVC from waste materials. The present application is to provide a recycled PVC material that is recycled from waste material, has physical properties equivalent to those of PVC material before use, effectively removes unnecessary impurities such as heavy metals, and at the same time beneficial additives remain, and a method for manufacturing the same. can In addition, the present application can obtain the recycled PVC material through an economical and environmentally friendly process that consumes little energy.

1 is a SEM (Scanning Electron Microscope) image of PVC particles recovered from waste.

2 is a SEM (Scanning Electron Microscope) image of synthesized PVC particles.

3 is a result of ¹ H NMR analysis of material recovered from waste.

4 is a result of ¹ H NMR analysis of general PVC.

Hereinafter, the present invention will be described in more detail through examples according to the present application, but the scope of the present invention is not limited to the following.

1. ¹ H NMR Analysis

¹ H NMR analysis of the PVC material was performed using a 400 MHz FT-NMR Spectrometer (model name: AVANCE III HD 400, manufacturer: Bruker Biospin) (measurement conditions: 400 MHz, solvent: THF (tetrahydrofuran) -D8)).

Based on the above analysis, the content of recycled PVC in the recycled PVC material was also confirmed.

2. 중금속 함량 측정 방법2. Heavy metal content measurement method

The content of heavy metals in the recycled PVC material was confirmed by inductively coupled plasma emission spectrometry (ICP-OES). The analysis was performed using Agilent's measuring device (Agilent's 5110 Series), and was performed according to the waste process test method (acid decomposition method) (KS C IEC62321-4 standard).

The heavy metal content is the result of measurement by taking measurement samples from the PVC material, randomly selecting 10 areas from the material, taking the same amount of samples from the selected areas, and measuring the heavy metal content. The arithmetic average of the results was taken as the representative value. The amount of the sample to be collected was the amount allowed by the measuring device.

3. 알루미늄 함량 측정 방법3. How to measure aluminum content

The aluminum content in the PVC material was measured using ICP-OES equipment (Technologies 5110 from Agilent) after acid decomposition of the measurement sample using a microwave equipment (TOPEX Microwave from Preekem) to prepare a pretreated sample.

Weigh about 0.3 g of PVC material (measurement sample) into a PTFE vessel, add 8 mL of nitric acid, 1 mL of hydrochloric acid, and 0.4 mL of hydrofluoric acid, and then raise the temperature step by step to 240 ° C in the microwave equipment to completely decompose acid. Then, ultrapure water was added to adjust the final volume to 50 mL to prepare a pretreated sample, and the Al content was measured for the sample.

Al content was measured according to the following procedure.

① Preparation of 0.02 mg/L to 0.2 mg/L Al standard solution

② Prepare a calibration curve at three wavelengths (167.019 nm, 237.312 nm and 396.152 nm) for the standard solution using ICP-OES.

③ Quantify the Al content in the pretreated sample using the calibration curve at the same wavelength as above

The Al content is a result measured by taking measurement samples from the PVC material, randomly selecting 10 areas from the material, taking the same amount of samples from the selected areas, and measuring the Al content. The arithmetic mean value of was taken as the representative value.

4. 프탈레이트 화합물 함량 측정 방법4. Method for measuring phthalate compound content

The content of the phthalate compound was measured by GC-MS (Gas Chromatography Mass Spectrometry) method. Measurements were performed using Agilent's 7890B (GC) and 5977B (MS) instruments. According to a known measurement method, the sample was dissolved in THF (Tetrahydrofuran), and after reprecipitation using alcohol, the concentration of the phthalate compound was measured.

The content of the phthalate is a result measured by taking measurement samples from the PVC material, randomly selecting 10 areas from the material, taking the same amount of samples from the selected areas, measuring the content, and then measuring the result. The arithmetic mean value of was taken as the representative value. The amount of the sample to be collected was the amount allowed by the measuring device.

5. 색좌표 측정 방법5. How to measure color coordinates

The color coordinates of the PVC material were measured using Spectro-guide gloss S equipment from BYK Gardner.

6. 재생 PVC에 대한 SEM 촬영6. SEM imaging of recycled PVC

SEM imaging of the recycled PVC material was performed using Hitachi's SU8010 equipment, and was taken at 100x magnification.

7. 열중량 분석(TGA) 분석7. Thermogravimetric analysis (TGA) analysis

Thermogravimetric analysis of the PVC material was performed using a TGA/DSC 3+ instrument from Mettler Toledo. The measurement was performed while raising the temperature in a temperature range from 30 °C to 1,000 °C at a heating rate of about 10 °C/min under a nitrogen (N ₂ ) atmosphere.

8. 양용매 및 비용매 함량 측정8. Measurement of good solvent and non-solvent content

The content of the good solvent and non-solvent contained in the recycled PVC material was confirmed by GC (Gas chromatography) analysis. Agilent's TDS3 and 7890A/5975C equipment were used as measuring instruments.

The content of the good solvent and non-solvent is the result of measurement by taking measurement samples from the PVC material, randomly selecting 10 areas from the material, and taking the same amount of samples from the selected area to measure the content The arithmetic average value of the results measured later was used as the representative value. The amount of the sample to be collected was the amount allowed by the measuring device.

9. 탄성 특성의 평가9. Evaluation of elastic properties

Tensile properties (tensile strength, tensile modulus, and tensile elongation) of specimens made of recycled PVC materials were evaluated using a tensile tester (Ametek Lloyd, Irx plus). It was evaluated according to the method (measurement conditions: Gauge Length 30mm, Width 25mm, Thickness 0.3mm).

10. 중량평균분자량/수평균분자량의 평가10. Evaluation of weight average molecular weight/number average molecular weight

Number average molecular weight (Mn) and weight average molecular weight were measured using GPC (Gel permeation chromatography). Put the recycled PVC material in a vial, and dilute it in tetrahydrofuran (THF) to a concentration of about 0.1% by weight. After that, the standard sample for calibration and the sample to be analyzed were filtered through a syringe filter (pore size: 0.45 ㎛) and then measured. The analysis program used ChemStation from Agilent technologies, and the weight average molecular weight (Mw) and number average molecular weight (Mn) were obtained by comparing the elution time of the sample with a calibration curve.

Instrument: 1260 Infinity from Agilent technologies

Column: Use 2 PLgel mixed A from Polymer laboratories

Solvent: THF

Column temperature: 35 ℃

Sample concentration: 1 mg/mL, 20 μL injection

Standard Sample: Polystyrene (PS-H EasiVial)

실시예 1.Example 1.

Waste windows made of PVC were used as waste, which is a raw material for PVC recycling. Foreign substances such as metal, glass, and adhesives present in the waste windows were first physically removed, and the waste windows from which the foreign substances were removed were firstly pulverized to a size of 2cmХ2cm with a grinder, and then secondarily pulverized to a size of 3mmХ3mm. The crushed waste windows were mixed with cyclohexanone (molar mass: about 98.15 g/mol, boiling point: about 155.6°C, water solubility (20°C): about 8.6 g/100mL, vapor pressure (20°C): about 5 mmHg). . During the mixing, the weight ratio of the waste windows and cyclohexanone was about 1:10 (waste windows:cyclohexanone). As described above, a mixture was prepared by mixing and stirring the waste windows and cyclohexanone. All of the above processes were performed at room temperature (about 25° C.).

The mixture was then mixed with a heavy metal scavenger. As a heavy metal removal agent, PAC (Poly Aluminum Chloride, manufactured by Samjusa Co., Ltd., 17% product) was used. The PAC was mixed with a 1% by weight aqueous solution of NaCl and used as a heavy metal scavenger.

The PAC was mixed with the NaCl aqueous solution in a weight ratio of 10:1 (PAC:NaCl aqueous solution) and used as a heavy metal removing agent. During the mixing process, the weight ratio of cyclohexanone and the heavy metal scavenger in the mixture was about 10:1 (cyclohexanone:heavy metal scavenger).

After the mixing, the mixture was stirred for about 1 hour and filtered through a sieve.

Thereafter, the filtered filtrate was allowed to stand to induce phase separation. All of the above processes were performed at room temperature (about 25° C.).

It was confirmed that the phase separation was performed, the phase-separated aqueous phase was removed, and the organic phase in which PVC was present was recovered. The organic phase was then mixed with ethanol (boiling point: about 78.37° C.), a non-solvent for PVC. The ratio of ethanol mixed in the above was controlled to about 200 to 250 parts by weight based on 100 parts by weight of the organic phase.

By the above mixing, PVC, which was dissolved and existed in the organic phase, was precipitated. The precipitated PVC was recovered and vacuum dried at a temperature of about 40° C. for about 15 hours to obtain a recycled PVC material.

3 is a ¹ H NMR spectrum of the recycled PVC material obtained in the above manner. From the figure, it can be seen that the peak (first peak, ①) derived from PVC is confirmed within the range of 4 ppm to 5 ppm, and the second peak (③) is confirmed within the range of about 1.1 ppm to 1.4 ppm. .

In the spectrum, the integral value of the first peak (the area of the peak found in the range of 4 ppm to 5 ppm) was about 1.00, and the integral value of the second peak (the area of the peak found in the range of about 1.1 ppm to 1.4 ppm) was about 1.00. area) was about 0.08. Accordingly, the ratio of the integral values (second peak/first peak) is about 0.08.

실시예 2.Example 2.

Recycled PVC was obtained in the same manner as in Example 1, except that during the mixing process with the heavy metal scavenger, the weight ratio of cyclohexanone and the heavy metal scavenger in the mixture was about 4:1 (cyclohexanone: heavy metal scavenger). .

비교예 1.Comparative Example 1.

Recycled PVC was prepared in the same manner as in Example 1, except that an aqueous solution of hydrochloric acid (pKa = about -6.3) was used as a heavy metal removal agent. At this time, the concentration of hydrochloric acid in the aqueous hydrochloric acid solution was about 1.1 M (molar concentration). The mixture and the aqueous hydrochloric acid solution were mixed, and during the mixing process, the weight ratio of cyclohexanone and the aqueous hydrochloric acid solution in the mixture was about 7:1 (cyclohexanone:hydrochloric acid).

비교예 2.Comparative Example 2.

Recycled PVC was prepared in the same manner as in Example 1, except that aluminum sulfate was used as a heavy metal removal agent. When the heavy metal remover (liquid) was mixed, the weight ratio of cyclohexanone and liquid in the mixture was about 7:1 (cyclohexanone:liquid).

The physical properties measured for the recycled PVC obtained in Examples and Comparative Examples are summarized in Table 1 below. In Table 1 below, Mw means the weight average molecular weight, and Mn means the number average molecular weight.

		실시예Example		비교예comparative example
		1One	22	1One	22
불순물 함량 (ppm)impurities content (ppm)	PbPb	1010	55	2020	260260
	Cd CD	00	00	00	22
	가소제 plasticizer	00	00	00	00
Al 함량(ppm)Al content (ppm)		약 200about 200	약 300about 300	약 100 미만less than about 100	약 100 미만less than about 100
사이클로헥사논함량(ppm)Cyclohexanone content (ppm)		약 400~500about 400 to 500	약 400~500about 400 to 500	약 400~500about 400 to 500	약 400~500about 400 to 500
에탄올 함량(ppm)Ethanol content (ppm)		약 400~500about 400 to 500	약 400~500about 400 to 500	약 400~500about 400 to 500	약 400~500about 400 to 500
색좌표 color coordinates	LL	92.292.2	92.292.2	9292	46.146.1
	aa	-0.45-0.45	-0.45-0.45	-0.3-0.3	9.49.4
	bb	3.583.58	3.583.58	5.045.04	15.4915.49
분자량 (×10000)Molecular Weight (×10000)	MwMw	16.416.4	16.416.4	15.815.8	16.416.4
분자량 (×10000)Molecular Weight (×10000)	MnMn	7.77.7	7.77.7	7.27.2	7.77.7

From the results of Table 1, it can be seen that the recycled PVC obtained by applying the method of the embodiment effectively removes heavy metals such as Pd or Cd and plasticizers, and exhibits excellent color characteristics.

Fig. 1 is a SEM photograph of reclaimed PVC particles recovered according to the method of Example 1, and it can be seen from the figure that the obtained reclaimed PVC is in a non-cluster particle state or primary particle state.

시험예 1.Test Example 1.

Specimen A was prepared using the recycled PVC material obtained in Example 1 as a raw resin material, and tensile strength, tensile modulus and elongation of the specimen were evaluated.

A stabilizer, CaCO ₃ and an additive were mixed with the recycled PVC material (raw resin material) of Example 1 at a weight ratio of 25:1.2:73:0.8 (PVC material:stabilizer:CaCO ₃ :additive), and a mixer (Brabender mixer) After kneading at 200 ° C., the kneaded material was press-worked at 200 ° C. to prepare a sheet material.

After that, specimen A was prepared by sequentially stacking a white sheet, transfer paper, and a transparent film commonly applied to window production on one side of the plate material.

On the other hand, specimen B was prepared using a mixture of the recycled PVC material obtained in Example 1 and general PVC (synthesized PVC rather than recycled PVC) as a raw resin material.

As the general PVC, LG Chem's general-purpose PVC, LS 100 product was used. 4 is a ¹ H NMR spectrum of the general PVC.

In the figure, it can be seen that in the spectrum of the general PVC, only the peak derived from PVC is confirmed, and the peak corresponding to the second peak of the recycled PVC material is not confirmed.

A raw resin material was prepared by mixing the recycled PVC material and normal PVC in a weight ratio of 6:4 (recycled PVC material: normal PVC). The stabilizer, CaCO ₃ and additives were mixed with the raw resin material in a weight ratio of 25:1.2:73:0.8 (raw resin material:stabilizer:CaCO ₃ :additive) in the same way as in the preparation of specimen A, and a mixer (Brabender mixer) ), and then kneaded at 200 ° C., the kneaded material was press-worked at 200 ° C. to prepare a plate having the same size as in specimen A. After that, specimen B was prepared by sequentially stacking a white sheet, a transfer paper, and a transparent film commonly applied to window production on one side of the plate material.

Specimen C is a mixture of the recycled PVC material of Example 1 and general PVC (synthesized PVC rather than recycled PVC) in a weight ratio of 1:9 (recycled PVC material: normal PVC) using a material as the raw resin material. It was manufactured in the same way as in the case of specimen B, except for specimen D, in which the general PVC (synthesized PVC, not recycled PVC) applied in specimens B and C was applied as a raw resin material instead of the recycled PVC material of Example 1. Except for the sample was prepared in the same way as in the case of sample A.

The evaluation results of the tensile properties of the specimens are shown in Table 2 below.

	시편APsalm A	시편BPsalm B	시편CPsalm C	시편DPsalm D
인장강도(MPa)Tensile strength (MPa)	19.9319.93	20.9720.97	23.3423.34	24.9324.93
인장탄성률(MPa)Tensile Modulus (MPa)	61986198	64786478	66106610	69836983
신율(mm)Elongation (mm)	3.273.27	3.363.36	3.393.39	3.943.94

From the results of Table 2, it can be seen that the elongation increases while the tensile strength and tensile modulus decrease as the content of the recycled PVC material increases. From these results, it can be seen that the material included in the recycled PVC material and forming the second peak improves brittleness, which is an inherent characteristic of PVC, and improves workability and flexibility of the material.

Claims

As a recycled polyvinyl chloride material recycled from waste,

Materials containing recycled polyvinyl chloride and aluminum.
The recycled polyvinyl chloride material according to claim 1, comprising at least 85% by weight of recycled polyvinyl chloride.
The recycled polyvinyl chloride material according to claim 1, wherein aluminum is contained in a compound represented by the following formula (1) or derived from a compound represented by the following formula (1):

[Formula 1]

[Al 2 (OH) n Cl 6-n ] m

In Formula 1, n is a number in the range of 1 to 5, and m is a number of 10 or less.
The recycled polyvinyl chloride material according to claim 1, comprising aluminum in a proportion within a range of greater than 0 ppm and less than or equal to 1000 ppm.
The recycled polyvinyl chloride material according to claim 1, further comprising a ketone or tetrahydrofuran.
The recycled polyvinyl chloride material according to claim 5, wherein the ketone has a molar mass in the range of 70 to 150 g/mol.
The recycled polyvinyl chloride material according to claim 5, wherein the ketone has a boiling point in the range of 130°C to 200°C.
The recycled polyvinyl chloride material according to claim 5, wherein the ketone has a water solubility of 15 g/100 mL or less at 20°C.
6. The recycled polyvinyl chloride material according to claim 5, wherein the ketone has a vapor pressure at 20 DEG C in the range of 1 to 10 mmHg.
6. The recycled polyvinyl chloride material according to claim 5, wherein the ketone is cyclohexanone.
The recycled polyvinyl chloride material according to claim 1, comprising heavy metals.
12. The recycled polyvinyl chloride material of claim 11 having a heavy metal content of less than 500 ppm.
12. The recycled polyvinyl chloride material of claim 11 having a heavy metal content of less than 100 ppm.
12. The recycled polyvinyl chloride material of claim 11 having a heavy metal content of less than 50 ppm.
12. The recycled polyvinyl chloride material of claim 11 having a heavy metal content of less than 10 ppm.
A resin molded body comprising the recycled polyvinyl chloride material according to any one of claims 1 to 15.
A window comprising the recycled polyvinyl chloride material according to any one of claims 1 to 15.