Plasticizer composition, method for preparing the same, and resin composition including the same

Abstract

This invention relates to a plasticizer composition comprising 2-ethylhexyl (2-hydroxyethyl) phthalate and di(2-ethylhexyl) phthalate, wherein the content of 2-ethylhexyl (2-hydroxyethyl) phthalate is 20 wt% or less based on the total plasticizer composition, and when the plasticizer composition is applied to a resin, it can improve mechanical properties, anti-migration properties and loss properties.

Description

[Technical Field]

[0001] This invention relates to a plasticizer composition comprising 2-ethylhexyl(2-hydroxyethyl) terephthalate and di(2-ethylhexyl) terephthalate, and a resin composition comprising the plasticizer composition. Cross-reference to related applications

[0002] This application claims the benefit of Korean Application No. 10-2022-0024952, filed with the Korean Intellectual Property Office on February 25, 2022, the disclosure of which is incorporated herein by reference in its entirety. [Previous Technology]

[0003] Typically, in plasticizers, alcohols react with polycarboxylic acids (such as phthalic acid and adipic acid) to form corresponding esters. Furthermore, considering domestic and international regulations concerning phthalate-based plasticizers, which are harmful to human health, ongoing research is being conducted on plasticizer compositions that can replace phthalate-based plasticizers, such as phthalate-based, adipic acid ester-based, and other polymer-based plasticizers.

[0004] At the same time, in all plastisol, calendering, or extrusion / injection composite industries that manufacture finished products such as flooring, wallpaper, soft and hard sheets, gloves, wires, hoses, and films, the demand for such environmentally friendly products is increasing. In order to enhance the quality characteristics, processability, and productivity of each finished product, appropriate plasticizers that take into account discoloration, migration, and mechanical properties should be used.

[0005] In these various application fields, according to the characteristics required by each industry, such as tensile strength, elongation, light resistance, migration, gelling properties or absorption rate, auxiliary raw materials (such as plasticizers, fillers, stabilizers, thickeners, dispersants, defoamers, foaming agents, etc.) are mixed into PVC resin.

[0006] For example, when using di(2-ethylhexyl) phthalate (DEHTP), which is relatively inexpensive and the most widely used plasticizer composition applicable to PVC, it has high hardness or sol viscosity, relatively slow absorption rate of plasticizer, and poor migration and stress migration.

[0007] In order to improve this, as a composition containing DEHTP, it is possible to consider using the product of the transesterification reaction with butanol as a plasticizer. However, while the plasticizing efficiency is improved, the mechanical properties are slightly reduced, and there will be local problems of plasticizer leakage due to heat or physical force.

[0008] In addition, ensuring environmental friendliness has recently become very important. In the industry, it is not only important to ensure the environmental friendliness of the final product itself, but also to ensure the environmental friendliness of the supply and demand of raw materials and processes. However, due to the conflict with the interests of ensuring cost competitiveness (which is the industry's top priority), there is a need to develop products that are both environmentally friendly and cost-competitive in terms of raw materials, preparation processes and final products. [Summary of the Invention]

[0009] Technical Issues

[0010] The present invention provides an environmentally friendly plasticizer composition by applying a composition containing 2-ethylhexyl (2-hydroxyethyl) p-phthalate and di(2-ethylhexyl) p-phthalate, which can be obtained during the decomposition process of polyethylene p-phthalate, to a plasticizer. This plasticizer is non-toxic to reproductive development and has properties equal to or higher than those of typical orthophthalate plasticizers.

[0011] Furthermore, the present invention provides a method for preparing plasticizer compositions that can economically and environmentally prepare plasticizer compositions with excellent physical properties using discarded polyethylene terephthalate as a raw material. Technical Means

[0012] To solve the above problems, the present invention provides a plasticizer composition, a method for preparing the plasticizer composition, and a resin composition comprising the plasticizer composition.

[0013] (1) The present invention provides a plasticizer composition comprising 2-ethylhexyl (2-hydroxyethyl) phthalate and di(2-ethylhexyl) phthalate, wherein the content of 2-ethylhexyl (2-hydroxyethyl) phthalate is 20 wt% or less based on the total plasticizer composition.

[0014] (2) In (1) above, the present invention provides a plasticizer composition wherein the content of 2-ethylhexyl (2-hydroxyethyl) phthalate is from 0.01 wt% to 15 wt%.

[0015] (3) In (1) or (2) above, the present invention provides a plasticizer composition wherein the weight ratio between 2-ethylhexyl (2-hydroxyethyl) phthalate and di(2-ethylhexyl) phthalate is 1:3 to 10000.

[0016] (4) In any one of (1) to (3) above, the present invention provides a plasticizer composition wherein the weight ratio between 2-ethylhexyl (2-hydroxyethyl) phthalate and di(2-ethylhexyl) phthalate is 1:5 to 1000.

[0017] (5) In any of (1) to (4) above, the present invention provides a plasticizer composition that further comprises one or more of a dimer compound represented by formula 1 to 3 below.

[0018]

[0019]

[0020]

[0021] (6) In (5) above, the present invention provides a plasticizer composition wherein the total content of the dimer compound in the composition is 2 wt% to 20 wt%.

[0022] (7) In (5) or (6) above, the present invention provides a plasticizer composition wherein the content of the dimer compound represented by Formula 1 above is from 0.01 wt% to 1 wt% in the composition.

[0023] (8) In any of (5) to (7) above, the present invention provides a plasticizer composition wherein the content of the dimer compound represented by Formula 3 above is from 0.3 wt% to 2.5 wt% in the composition.

[0024] (9) In any of (5) to (8) above, the present invention provides a plasticizer composition wherein the weight ratio between the dimer compound and 2-ethylhexyl (2-hydroxyethyl) phthalate is 1:0.001 to 5 in the composition.

[0025] (10) In any of (5) to (9) above, the present invention provides a plasticizer composition wherein the weight ratio between the dimer compound and di(2-ethylhexyl) phthalate is 1:2.0 to 99.0 in the composition.

[0026] (11) The present invention provides a method for preparing a plasticizer composition, wherein the method includes a step of mixing polyethylene terephthalate and 2-ethylhexanol in the presence of a catalyst to carry out a transesterification reaction, wherein the product of the transesterification reaction includes 2-ethylhexyl (2-hydroxyethyl) terephthalate and di(2-ethylhexyl) terephthalate.

[0027] (12) In (11) above, the present invention provides a method for preparing a plasticizer composition, wherein the polyethylene terephthalate is mixed in an amount of 80 wt% or less relative to the sum of the contents of polyethylene terephthalate and 2-ethylhexanol.

[0028] (13) In (11) or (12) above, the present invention provides a method for preparing a plasticizer composition, wherein the polyethylene terephthalate comprises discarded and recycled polyethylene terephthalate.

[0029] (14) The present invention provides a resin composition comprising 100 parts by weight of resin and 5 to 150 parts by weight of a plasticizer composition according to any one of (1) to (10).

[0030] (15) In (14) above, the present invention provides a resin composition wherein the resin is selected from one or more of the group consisting of: linear vinyl chloride polymers, paste-like vinyl chloride polymers, ethylene-vinyl acetate copolymers, ethylene polymers, propylene polymers, polyketones, polystyrene, polyurethanes, polylactic acid, natural rubber, and synthetic rubber. Advantages

[0031] When used in resin compositions, the plasticizer composition according to one embodiment of the present invention is an environmentally friendly material compared to typical plasticizers. It is non-toxic to reproduction and development and can improve mechanical properties, migration resistance, stress migration and absorption rate. This top-down preparation method utilizes waste and is therefore an environmentally friendly preparation method. At the same time, it can have very good cost competitiveness.

Implementation Method

[0032] It is understood that the words or terms used in the specification and claims of this invention should not be construed as having the meanings defined in commonly used dictionaries. It is further understood that, based on the principle that inventors may appropriately define such words or terms to best interpret the invention, such words or terms should be construed as having meanings consistent with their meanings in the context of the relevant technical field and in the technical concept of the invention.

[0033] Term Definitions

[0034] As used herein, the term "composition" includes not only reaction products and decomposition products formed from the materials of the corresponding composition, but also mixtures of materials containing the corresponding composition.

[0035] As used herein, the term "linear vinyl chloride polymer" can refer to one type of vinyl chloride polymer that is polymerized by means of suspension polymerization, bulk polymerization, or similar methods. This polymer consists of porous particles with multiple pores, and has a size of tens to hundreds of micrometers, is non-cohesive, and has excellent flowability.

[0036] As used herein, the term "paste vinyl chloride polymer" refers to a type of vinyl chloride polymer that is polymerized through methods such as micro-suspension polymerization, micro-seed polymerization, and emulsion polymerization. This polymer consists of non-porous, fine particles with a size ranging from tens to thousands of nanometers, exhibiting cohesiveness and poor flowability.

[0037] Regardless of whether the terms "comprising" and "having" and their derivatives specifically disclose them, they are not intended to exclude the presence of any additional components, steps, or procedures. To avoid any uncertainty, unless otherwise indicated, all components claimed by the use of the term "comprising" may contain any additional additives, auxiliaries, or compounds, whether polymers or otherwise. Conversely, the term "substantially composed of" excludes any other components, steps, or procedures from the scope of any subsequent description, except where it is unnecessary for operability. The term "composed of" excludes any components, steps, or procedures not specifically identified or listed.

[0038] Measurement Method

[0039] In this specification, the content analysis of the components in the composition is performed by gas chromatography, and the analysis is performed using an Agilent gas chromatography apparatus (product name: Agilent 7890 GC, column: HP-5, carrier gas: helium (flow rate: 2.4 mL / min), detector: FID, injection volume: 1 µL, initial value: 70℃ / 4.2 min, final value: 280℃ / 7.8 min, program rate: 15℃ / min).

[0040] In this specification, "tensile strength" is the point at which the specimen breaks after being stretched at a crosshead speed of 200 mm / min (1T) using the ASTM D638 method with a UTM (manufacturer: Instron, model name: 4466) test apparatus, and then calculated by Equation 1 below.

[0041] [Equation 1] Tensile strength (kgf / cm2) = Load value (kgf) / Thickness (cm) × Width (cm)

[0042] In this specification, "elongation rate" is the point at which the specimen breaks after being stretched by a crosshead at a speed of 200 mm / min (1T) using a UTM according to the ASTM D638 method, and then calculated by Equation 2 below.

[0043] [Equation 2] Elongation (%) = Length after elongation / Initial length × 100

[0044] In this specification, "migration loss" can be measured according to KSM-3156. Specifically, a test specimen with a thickness of 1 mm is obtained, and absorbent sheets that can move to both sides of the test specimen to absorb organic material discharging onto the surface of the test specimen are added. Then, a plate covering the entire test specimen is attached to it to apply a load of 1 kgf / cm². The test specimen is placed in a hot air circulating oven (80°C) for 72 hours, then removed from the oven and cooled to room temperature for 4 hours. Next, the plates and absorbent sheets attached to both sides of the test specimen are removed, and the weight of the specimen before and after placing it in the oven is measured to calculate the migration loss according to Equation 3 below.

[0045] [Equation 3] Migration loss (%) = {[(Initial sample weight) – (Sample weight after standing in the oven)] / (Initial sample weight)} × 100

[0046] In this specification, "volatile loss" is obtained by treating the sample at 80°C for 72 hours and then measuring the weight of the sample.

[0047] [Equation 4] Volatilization loss (%) = {[(Initial sample weight) – (Sample weight after treatment)] / (Initial sample weight)} × 100

[0048] Under the various measurement conditions mentioned above, the detailed conditions such as temperature, rotation speed, and time may vary slightly depending on the circumstances, and when the specific conditions are different, the measurement methods and conditions shall be indicated separately.

[0049] In this specification, "absorption rate" is the time taken from mixing the resin and plasticizer with each other using a planetary mixer (Brabender, P600) until the torque of the mixer stabilizes under conditions of 77°C and 60 rpm.

[0050] Under the various measurement conditions mentioned above, the detailed conditions such as temperature, rotation speed, and time may vary slightly depending on the circumstances, and when the specific conditions are different, the measurement methods and conditions shall be indicated separately.

[0051] The present invention will be described in more detail below to aid in understanding the invention.

[0052] Plasticizer composition

[0053] The present invention provides a plasticizer composition comprising 2-ethylhexyl (2-hydroxyethyl) phthalate and di(2-ethylhexyl) phthalate, wherein the content of 2-ethylhexyl (2-hydroxyethyl) phthalate is 20 wt% or less based on the total plasticizer composition.

[0054] A plasticizer composition comprising 2-ethylhexyl (2-hydroxyethyl) phthalate and di(2-ethylhexyl) phthalate can be obtained from a product produced by transesterification reaction between polyethylene terephthalate (hereinafter, PET) and 2-ethylhexanol.

[0055] Generally, as a means of obtaining di(2-ethylhexyl) phthalate, which is used as a typical general-purpose plasticizer, there are several issues: PET reacts with 2-ethylhexanol, but this produces a large number of byproducts, and it is difficult to separate the bis(2-hydroxyethyl) phthalate or 2-ethylhexyl(2-hydroxyethyl) phthalate produced during the reaction process from di(2-ethylhexyl) phthalate. Furthermore, bis(2-hydroxyethyl) phthalate and 2-ethylhexyl(2-hydroxyethyl) phthalate are alcohol compounds containing hydroxyl groups in their intramolecular structure, which may lead to another problem: side reactions with the target product, di(2-ethylhexyl) phthalate, may occur. Therefore, as a method for preparing di(2-ethylhexyl) phthalate, almost every manufacturer uses the direct transesterification reaction of phthalic acid with 2-ethylhexanol or the transesterification reaction of dimethyl phthalate with 2-ethylhexanol, rather than using PET as a raw material.

[0056] However, in this invention, it has been demonstrated that it is possible to provide plasticizer compositions with improved performance compared to typical plasticizer products by focusing on the function of 2-ethylhexyl (2-hydroxyethyl) p-phthalate, which is generally considered an impurity and therefore a target for removal, and allowing 2-ethylhexyl (2-hydroxyethyl) p-phthalate to be included in the plasticizer composition in a predetermined amount rather than being removed. Although 2-ethylhexyl (2-hydroxyethyl) p-phthalate is not easily separated from di(2-ethylhexyl) p-phthalate, it is used to solve the compression migration problem of di(2-ethylhexyl) p-phthalate, i.e., the problem of plasticizer release due to heat or pressure. In particular, due to the presence of hydroxyl groups in the intramolecular structure, 2-ethylhexyl (2-hydroxyethyl) p-phthalate can bind more firmly to the resin to be mixed and can play a role in holding the main component of the plasticizer composition, di(2-ethylhexyl) p-phthalate, in order to prevent it from being expelled from the resin.

[0057] According to one embodiment of the present invention, the content of 2-ethylhexyl (2-hydroxyethyl) phthalate may be 20 wt% or less based on the total plasticizer composition. Examplely, based on the total plasticizer composition, the content of 2-ethylhexyl (2-hydroxyethyl) p-phthalate may be 0.01 wt% or more, 0.05 wt% or more, 0.06 wt% or more, 0.08 wt% or more, 0.10 wt% or more, 0.50 wt% or more, 1.0 wt% or more, 2.0 wt% or more, 3.0 wt% or more, 4.0 wt% or more, 4.5 wt% or more, 4.9 wt% or more, 5.0 wt% or more, 5.5 wt% or more, 7.5 wt% or more, 8.0 wt% or more, and 20.0 wt% or less, 19.5 wt% or less, 19.0 wt% or less, 18.0 wt% or less, 17.0 wt% or less, 16.0 wt% or less, 15.0 wt% or less, 14.9 wt% or less, and so on. wt% or less, 14.5 wt% or less, 13.0 wt% or less, 12.8 wt% or less, 12.5 wt% or less, 12.4 wt% or less, 12.0 wt% or less, 11.7 wt% or less, 11.5 wt% or less, 11.3 wt% or less, 11.0 wt% or less, 10.5 wt% or less, 10.0 wt% or less, 9.5 wt% or less, 9.3 wt% or less, 8.0 wt% or less, 8.5 wt% or less, 8.0 wt% or less, 7.5 wt% or less, 7.2 wt% or less, 7.0 wt% or less, 6.5 wt% or less, 6.0 wt% or less, 5.5 wt% or less, 5.0 wt% or less, 4.5 wt% or less, 4.0 The content of 2-ethylhexyl (2-hydroxyethyl) p-phthalate may be from 0.01 wt% to 15 wt%, based on the total plasticizer composition. Furthermore, the weight ratio between 2-ethylhexyl (2-hydroxyethyl) p-phthalate and di(2-ethylhexyl) p-phthalate may be from 1:3 to 10000, more preferably from 1:5 to 1:2000 or from 1:5 to 1:1000.When the content of 2-ethylhexyl (2-hydroxyethyl) p-phthalate in the plasticizer composition is too small, the effect of 2-ethylhexyl (2-hydroxyethyl) p-phthalate in improving anti-migration properties may not be significant. Conversely, when the content of 2-ethylhexyl (2-hydroxyethyl) p-phthalate is too large, the content of di(2-ethylhexyl) p-phthalate becomes relatively small, resulting in poor volatilization loss and an excessively increased absorption rate. This may cause instability in the blending and finishing processes with the resin, thereby potentially deteriorating the overall heat resistance of the resin composition or the finished product obtained from the resin composition. In particular, when 2-ethylhexyl (2-hydroxyethyl) p-phthalate is included as a major component in the plasticizer composition, its relatively low molecular weight may make it difficult to blend with the resin, and subsequent rolling processes may not be able to proceed smoothly. When the content of 2-ethylhexyl (2-hydroxyethyl) phthalate meets the above-mentioned preferred range, appropriate volatilization loss and appropriate absorption rate can be achieved, making it possible to provide a plasticizer composition with excellent heat resistance and stable blendability with resin compositions.

[0058] According to one embodiment of the present invention, the plasticizer composition of the present invention may further include one or more of the dimer compounds represented by the following formulas 1 to 3.

[0059]

[0060]

[0061]

[0062] In this invention, a dimer compound having a (p-phthalate or m-phthalate)-(ethylene glycol)-(p-phthalate or m-phthalate) structure, which is one of the byproducts, like the aforementioned 2-ethylhexyl (2-hydroxyethyl) phthalate, is controlled to be included in the plasticizer composition at a predetermined content, so that it has been shown that it is possible to provide a plasticizer composition with improved performance compared to typical plasticizer products. Because recycled polyethylene terephthalate (PET) is used as a raw material during the preparation process of the plasticizer composition and because a small amount of high-purity m-phthalic acid remains after the preparation of PET, m-phthalate may be produced.

[0063] Depending on the reaction time or many reaction conditions used in the depolymerization process of PET, such dimer compounds can be prepared in various forms and amounts, and since compounds with this structure are included in the plasticizer composition together with para-phthalate plasticizers, it is possible to compensate for the compression migration of typical para-phthalate plasticizers.

[0064] For example, in the process of synthesizing di(2-ethylhexyl) phthalate, in which the monomer is synthesized by reaction between 2-ethylhexanol and PET, a dimer compound in which 2-ethylhexanol is attached to the ends of the two p-phthalic acids can be produced, and the dimer compound can be included in the final plasticizer composition.

[0065] The above-described process for forming a dimer compound is one example. In addition to the above-described process, dimer compounds can also be formed in various combinations by various reactions between 2-ethylhexyl (2-hydroxyethyl) phthalate and 2-ethylhexyl (2-hydroxyethyl) m-phthalate.

[0066] Furthermore, the contents of di(2-ethylhexyl) phthalate, 2-ethylhexyl(2-hydroxyethyl) phthalate, and dimer compounds can be controlled by intentionally controlling the transesterification reaction in the above preparation method. At the same time, when the reaction time is controlled during the transesterification reaction, a relatively large amount of byproducts such as trimer and / or tetramer compounds and dimer compounds may be produced depending on the reaction time. Since the byproducts maintain the final processing physical properties of the entire plasticizer composition of di(2-ethylhexyl) phthalate and 2-ethylhexyl(2-hydroxyethyl) phthalate at a useful level without deterioration, the reaction product containing the above-mentioned byproducts can be used as a plasticizer composition.

[0067] In addition, the content of the dimer compound can be determined according to the amount of catalyst used in the preparation method, the amount of 2-ethylhexanol to be added, the reaction pressure and temperature, the reaction time, etc., and in particular, the content of condensation polymer and dimer may decrease as the amount of 2-ethylhexanol to be added increases. In the plasticizer composition provided by the present invention, the total content of the dimer compound in the composition may be from 2.0 wt% to 20.0 wt%, and exemplarily, the total content of the dimer compound in the composition may be 2.0 wt% or more, 3.0 wt% or more, 4.0 wt% or more, 5.0 wt% or more, 6.0 wt% or more, 7.0 wt% or more, 8.0 wt% or more, and 20.0 wt% or less, 19.0 wt% or less, 18.0 wt% or less, 17.0 wt% or less, 16.0 wt% or less, 15.0 wt% or less, 14.0 wt% or less, 13.0 wt% or less, 12.0 wt% or less, or 10.0 wt% or less. Preferably, the total content of the dimer compound in the composition may be from 2.0 wt% to 15.0 wt%. When the content of the dimer compound is controlled within the above range, it is possible to provide a plasticizer composition with migration and volatilization loss properties equal to or higher than those of typical plasticizer products, and with excellent mechanical properties (such as tensile strength and tensile residual rate) and stress resistance.

[0068] Furthermore, the compounds represented by Formulas 1 to 3 above may coexist in the plasticizer composition. In the plasticizer composition provided by the present invention, the content of the dimer compound represented by Formula 1 above in the composition may be from 0.01 wt% to 1 wt%, the content of the dimer compound represented by Formula 2 above may be from 1.5 wt% to 17.0 wt%, and the content of the dimer compound represented by Formula 3 above may be from 0.3 wt% to 2.5 wt%.

[0069] Specifically, the content of the dimer compound represented by Formula 1 above may be 0.01 wt% or more, 0.02 wt% or more, 0.03 wt% or more, 0.04 wt% or more, 0.05 wt% or more, 0.10 wt% or more, 0.20 wt% or more, 0.40 wt% or more, and 1.0 wt% or less, 0.90 wt% or less, 0.80 wt% or less, 0.70 wt% or less, 0.60 wt% or less, or 0.50 wt% or less.

[0070] Specifically, the content of the dimer compound represented by Formula 2 above may be 1.5 wt% or more, 1.7 wt% or more, 1.8 wt% or more, 2.0 wt% or more, 2.5 wt% or more, 2.7 wt% or more, 3.0 wt% or more, 3.5 wt% or more, 3.7 wt% or more, 4.0 wt% or more, 5.0 wt% or more, and 17.0 wt% or less, 16.0 wt% or less, 15.0 wt% or less, 14.0 wt% or less, 13.0 wt% or less, 12.0 wt% or less, 11.0 wt% or less, 10.0 wt% or less, 9.0 wt% or less, 8.0 wt% or less, 7.0 wt% or less, 6.0 wt% or less, 7.0 wt% or less, or 6.0 wt%. wt% or less.

[0071] In addition, specifically, the content of the dimer compound represented by Formula 3 above may be 0.3 wt% or more, 0.4 wt% or more, 0.5 wt% or more, 0.7 wt% or more, 1.0 wt% or more, 1.1 wt% or more, 1.2 wt% or more, 1.3 wt% or more, 1.5 wt% or more, and 2.5 wt% or less, 2.4 wt% or less, 2.3 wt% or less, 2.1 wt% or less, 2.0 wt% or less, 1.7 wt% or less, 1.5 wt% or less, 1.3 wt% or less, 1.2 wt% or less, or 1.1 wt% or less.

[0072] When the content of each of the dimer compounds represented by Formulas 1 to 3 above meets the above range, it is possible to obtain the effect of improving the resistance to migration and volatilization loss in the resin processing properties.

[0073] In addition, the weight ratio between the dimer compound and 2-ethylhexyl (2-hydroxyethyl) phthalate in the composition may be from 1:0.001 to 5.0, and exemplarily, 1:0.01 or more, 0.02 or more, 0.05 or more, 0.1 or more, 0.2 or more, 0.5 or more, 0.7 or more, 1.0 or more, 1.5 or more, and 5.0 or less, 4.7 or less, 4.5 or less, 4.2 or less, 4.0 or less, 3.7 or less, 3.5 or less, 3.2 or less, 3.0 or less, 2.7 or less, 2.5 or less, 2.3 or less, 2.0 or less, 1.7 or less, 1.5 or less, 1.2 or less, 1.0 or less, or 0.8 or less. Preferably, the weight ratio between the dimer compound and 2-ethylhexyl (2-hydroxyethyl) p-phthalate can be from 1:0.01 to 0.8. When the weight ratio between the dimer compound and 2-ethylhexyl (2-hydroxyethyl) p-phthalate meets the above range in the plasticizer composition, the effect of improving anti-migration properties may be excellent, and the volatilization loss and absorption rate may be excellent to facilitate blending with the resin and the subsequent rolling process, thereby potentially increasing processing stability.

[0074] Furthermore, the weight ratio between the dimer compound and di(2-ethylhexyl) phthalate in the composition may be from 1:2.0 to 99.0, and exemplarily, 1:2.0 or more, 2.5 or more, 2.7 or more, 3.0 or more, 3.5 or more, 4.0 or more, 4.5 or more, 5.0 or more, 6.0 or more, 7.0 or more, 9.0 or more, 10.0 or more, 12.0 or more, or 15.0. More, 20.0 or more, 25.0 or more, 27.0 or more, 30.0 or more, 35.0 or more, and 99.0 or less, 95.0 or less, 92.0 or less, 90.0 or less, 85.0 or less, 80.0 or less, 75.0 or less, 70.0 or less, 65.0 or less, 60.0 or less, 55.0 or less, 50.0 or less, 45.0 or less, or 40.0 or less. Preferably, the weight ratio between the dimer compound and di(2-ethylhexyl) p-phthalate in the composition can be from 1:2.7 to 45. When the weight ratio between the dimer compound and di(2-ethylhexyl) p-phthalate falls within the above range, the effect of improving anti-migration achieved by including the dimer compound in the plasticizer composition can be maximized.

[0075] A method for hydrogenating the plasticizer composition of the present invention can be applied. The present invention provides a plasticizer composition comprising cyclohexane-1,4-dicarboxylic acid 2-ethylhexyl (2-hydroxyethyl) ester and cyclohexane-1,4-dicarboxylic acid di(2-ethylhexyl) ester, wherein the content of cyclohexane-1,4-dicarboxylic acid 2-ethylhexyl (2-hydroxyethyl) ester is 20 wt% or less based on the total plasticizer composition. Additionally, the plasticizer composition may further comprise a hydrogenated form of a dimer compound represented by formulas 1 to 3.

[0076] A plasticizer composition comprising 2-ethylhexyl (2-hydroxyethyl) cyclohexane-1,4-dicarboxylic acid and di(2-ethylhexyl) cyclohexane-1,4-dicarboxylic acid can be obtained by subjecting a product produced by a transesterification reaction between polyethylene terephthalate (hereinafter, PET) and 2-ethylhexanol to a hydrogenation reaction, wherein the order of the transesterification reaction and the hydrogenation reaction can be reversed. The product comprises the aforementioned 2-ethylhexyl (2-hydroxyethyl) phthalate and di(2-ethylhexyl) phthalate, and may further comprise dimer compounds of formulas 1 to 3.

[0077] Plasticizer compositions can significantly improve migration and loss properties while eliminating environmental issues, and can achieve products with significantly improved light and heat resistance compared to typical commercial products.

[0078] Method for preparing plasticizer composition

[0079] The present invention provides a method for preparing the above-mentioned plasticizer composition.

[0080] Specifically, the present invention includes a method for preparing a plasticizer composition, wherein the method comprises a step of mixing polyethylene terephthalate and 2-ethylhexanol in the presence of a catalyst to carry out a transesterification reaction, wherein the product of the transesterification reaction comprises 2-ethylhexyl (2-hydroxyethyl) terephthalate and di(2-ethylhexyl) terephthalate. Furthermore, the product may further comprise one or more of the dimer compounds represented by formulas 1 to 3 above.

[0081] PET and 2-ethylhexanol are converted into a composition containing the two components through a transesterification reaction. Specifically, PET is represented by the following formula a.

[0082]

[0083] In the transesterification reaction of PET and 2-ethylhexanol, 2-ethylhexanol reacts with the ester group present in PET, thereby releasing the polymer chain of PET, and the ratio of the two components can be controlled depending on how the reaction is controlled, and it is important that not only the ratio of the two components but also the ratio of the dimer compound are controlled within the above range.

[0084] Based on the sum of the contents of PET and 2-ethylhexanol, PET may be contained in an amount of 80 wt% or less, preferably 60 wt% or less, more preferably 50 wt%, 40 wt%, or 35 wt% or less. When the PET content is within the above range, the amount of 2-ethylhexanol added is sufficient to minimize side reactions and maximize the desired transesterification reaction between PET and 2-ethylhexanol. In particular, when the PET content is within the above range, the composition obtained through the preparation process satisfies the above-mentioned preferred content conditions, thus having the advantage of directly preparing plasticizer compositions with excellent physical properties while minimizing post-processing after the preparation process.

[0085] Meanwhile, the PET may contain 50 wt% or more, preferably 60 wt% or more, and more preferably 70 wt% or more of waste PET. Even with the use of waste PET, the component ratio in the final product remains unchanged, making it possible to use waste PET in the entire quantity, provided that the color or impurity content of the plasticizer can be controlled. Since the use of waste PET as described above is cost-competitive compared to the production of di(2-ethylhexyl) p-phthalate from p-phthalic acid or dimethyl p-phthalate, it can reduce energy consumption in the preparation of p-phthalic acid or dimethyl p-phthalate and prevent environmental pollution, thus making a significant contribution to environmental improvement.

[0086] In the preparation method according to one embodiment of the present invention, byproducts generated during the reaction, such as ethylene glycol, can be recovered outside the system, although some of the ethylene glycol may remain in the reaction system. When some ethylene glycol remains in the reaction system and participates in the reaction, appropriate levels of 2-ethylhexyl (2-hydroxyethyl) p-phthalate and dimer compounds of formulas 1 to 3 above can be formed from the ethylene glycol remaining in the reaction system. Since 2-ethylhexyl (2-hydroxyethyl) p-phthalate and dimer compounds of formulas 1 to 3 contribute to the improvement of the performance of the plasticizer composition, it is not necessary to consume separate energy to remove the formed 2-ethylhexyl (2-hydroxyethyl) p-phthalate and dimer compounds of formulas 1 to 3, thus making it possible to operate the preparation process economically. In particular, since ethylene glycol is used as a reactant to form 2-ethylhexyl (2-hydroxyethyl) p-phthalate and dimer compounds of formulas 1 to 3, the content of ethylene glycol in the final composition is naturally greatly reduced, thus having the advantage of simplifying the separation process.

[0087] An example of a catalyst may be selected from one or more of the following: acid catalysts, such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butyric acid, and alkyl sulfuric acid; metal salts, such as aluminum lactate, lithium fluoride, potassium chloride, cesium chloride, calcium chloride, ferric chloride, and aluminum phosphide; metal oxides, such as heteropoly acid; natural / synthetic zeolites; cation and anion exchange resins; catalysts containing choline compounds, such as choline hydroxide, choline bicarbonate, choline chloride, stannate choline, dihydrocholine citrate, and choline sulfate; organometallic compounds, such as alkyl titanates (such as tetraalkyl titanate) or polymers thereof; and organometallic compounds containing zirconium or tin. Preferably, the catalyst may be a tetraalkyl titanate.

[0088] The amount of catalyst to be used may vary depending on its type. As an example, based on 100 wt% of reactants, a homogeneous catalyst system may be used in amounts of 0.01 wt% to 5 wt%, 0.01 wt% to 3 wt%, 1 wt% to 5 wt%, or 2 wt% to 4 wt%, while based on 100 wt% of reactants, a heterogeneous catalyst system may be used in amounts of 5 wt% to 200 wt%, 5 wt% to 100 wt%, 20 wt% to 200 wt%, or 20 wt% to 150 wt%.

[0089] According to one embodiment of the present invention, the transesterification reaction is preferably carried out at a reaction temperature of 120°C to 240°C, more preferably 135°C to 230°C, and even more preferably 141°C to 220°C for 10 minutes to 12 hours, more preferably 30 minutes to 10 hours, and even more preferably 1 to 8 hours. Within the above temperature and time range, the composition ratio of the final plasticizer composition can be efficiently controlled. In this case, the reaction time can be calculated from the time the temperature of the reactants is increased until the reaction temperature is reached.

[0090] Furthermore, this method may further include a step of removing unreacted 2-ethylhexanol and the reaction byproduct ethylene glycol after the transesterification reaction. Since ethylene glycol has high solubility in water, it can be removed by neutralization and washing with water after the reaction, and residual 2-ethylhexanol can be removed by extractive distillation after neutralization and washing with water. Through the above steps, a plasticizer composition that meets the desired components and composition ratio can be prepared.

[0091] According to another embodiment of the present invention, a resin composition comprising the aforementioned plasticizer composition and resin is provided.

[0092] As the resin, resins known in the art can be used. For example, a mixture selected from one or more of the following groups can be used as the resin: linear vinyl chloride polymers, paste-like vinyl chloride polymers, ethylene-vinyl acetate copolymers, ethylene polymers, propylene polymers, polyketides, polystyrene, polyurethane, polylactic acid, natural rubber, synthetic rubber, and thermoplastic elastomers. However, the present invention is not limited thereto.

[0093] Based on 100 parts by weight of resin, the plasticizer composition system may contain 5 to 150 parts by weight, preferably 5 to 130 parts by weight, or 10 to 120 parts by weight.

[0094] Generally speaking, the resin in which the plasticizer composition is used can be made into a resin product through melt processing or plastisol processing, and the resin processed by melt processing and the resin processed by plastisol processing can be produced differently depending on the polymerization method.

[0095] For example, when vinyl chloride polymers are used in melt processing, solid resin particles with a large average particle size are used, produced by processes such as suspension polymerization, and such vinyl chloride polymers are called linear vinyl chloride polymers. When used in plastisol processing, sol-like resins with tiny resin particles are used, produced by processes such as emulsification polymerization, and such vinyl chloride polymers are called paste vinyl chloride resins.

[0096] In the case of linear vinyl chloride polymers, the plasticizer is preferably contained in the range of 5 to 80 parts by weight based on 100 parts by weight of polymer, while in the case of paste-like vinyl chloride polymers, the plasticizer is preferably contained in the range of 40 to 120 parts by weight based on 100 parts by weight of polymer.

[0097] The resin composition may further include filler. Based on 100 parts by weight of resin, the filler may be 0 to 300 parts by weight, more preferably 50 to 200 parts by weight, and even more preferably 100 to 200 parts by weight.

[0098] The packing material may be any packing material known in the art and is not particularly limited. For example, the packing material may be a mixture selected from one or more of the following: silica, magnesium carbonate, calcium carbonate, pyrocarbonate, talc, magnesium hydroxide, titanium dioxide, magnesium oxide, calcium hydroxide, aluminum hydroxide, aluminum silicate, magnesium silicate, and barium sulfate.

[0099] In addition, if necessary, the resin composition may further include other additives, such as stabilizers. Based on 100 parts by weight of resin, other additives (such as stabilizers) may be 0 to 20 parts by weight, preferably 1 to 15 parts by weight.

[0100] The stabilizer may be, for example, a calcium-zinc (Ca-Zn) stabilizer such as a calcium-zinc complex stearate, or a barium-zinc (Ba-Zn) stabilizer, but is not particularly limited thereto.

[0101] As described above, the resin composition can be applied to both melt processing and plastisol processing. For example, calendering, extrusion, or injection processing can be used as melt processing, while coating processing can be used as plastisol processing.

[0102] Example

[0103] The present invention will now be described in detail with reference to embodiments. However, embodiments of the present invention may be modified in various other forms, and the scope of the present invention should not be construed as limited to the embodiments described below. The embodiments of the present invention are provided to fully describe the present invention to those skilled in the art.

[0104] Example 1

[0105] 1.5 g of catalyst (TnBT), 500 g of discarded polyethylene terephthalate (PET), and 1220 g of 2-ethylhexanol were added to a reactor equipped with a stirrer, condenser, and decanter. The reactor was then subjected to a transesterification reaction for 3 to 8 hours under a nitrogen atmosphere and at a reaction temperature of 150°C to 230°C. After the reaction was completed, unreacted 2-ethylhexanol was removed by vacuum decompression. Next, 100 g of a 3 wt% aqueous sodium hydroxide solution was added to neutralize the catalyst, and a small amount of unreacted 2-ethylhexanol was removed by distillation. Through the above steps, a composition containing 12.4 wt% 2-hydroxyethyl(2-ethylhexyl) PET and 71 wt% di(2-ethylhexyl) PET (DEHTP) was obtained. The remaining components of the composition, excluding these two components, contained byproducts generated during the reaction process, and these byproducts contained dimer compounds in the amounts shown in Table 1 below.

[0106] Example 2

[0107] By controlling the input amount of 2-ethylhexanol and the reaction time, compositions comprising 7.2 wt% and 78.5 wt% of 2-hydroxyethyl(2-ethylhexyl) p-phthaloate and di(2-ethylhexyl) p-phthaloate (DEHTP) were obtained using the same method as in Example 1. The remaining components in the compositions, excluding these two components, contain byproducts generated during the reaction process, and these byproducts contain dimer compounds in the amounts shown in Table 1 below.

[0108] Example 3

[0109] By controlling the input amount of 2-ethylhexanol and the reaction time, compositions comprising 4.9 wt% and 90.3 wt% of 2-hydroxyethyl(2-ethylhexyl) p-phthaloate and di(2-ethylhexyl) p-phthaloate (DEHTP), respectively, were obtained using the same method as in Example 1. The remaining components in the compositions, excluding these two components, contain byproducts generated during the reaction process, and these byproducts contain dimer compounds in the amounts shown in Table 1 below.

[0110] Example 4

[0111] By controlling the input amount of 2-ethylhexanol and the reaction time, compositions containing 0.06 wt% and 95.8 wt% of 2-hydroxyethyl(2-ethylhexyl) p-phthaloate and di(2-ethylhexyl) p-phthaloate (DEHTP), respectively, were obtained using the same method as in Example 1. The remaining components in the compositions, excluding these two components, contain byproducts generated during the reaction process, and these byproducts contain dimer compounds in the amounts shown in Table 1 below.

[0112] Example 5

[0113] By controlling the input amount of 2-ethylhexanol and the reaction time, compositions comprising 19.1 wt% and 58.9 wt% of 2-hydroxyethyl(2-ethylhexyl) p-phthaloate and di(2-ethylhexyl) p-phthaloate (DEHTP), respectively, were obtained using the same method as in Example 1. The remaining components in the compositions, excluding these two components, contain byproducts generated during the reaction process, and these byproducts contain dimer compounds in the amounts shown in Table 1 below.

[0114] Comparative Example 1

[0115] Di(2-ethylhexyl) phthalate (DEHP), a product of LG Chem, is used as a plasticizer component.

[0116] Comparative Example 2

[0117] Except for adding 1400 g of 2-ethylhexanol to remove all of the 2-hydroxyethyl(2-ethylhexyl) p-phthaloate from the composition, a composition containing 99.9 wt% di(2-ethylhexyl) p-phthaloate (DEHTP) was obtained by the same method as in Example 1.

[0118] Comparative Example 3

[0119] By controlling the input amount of 2-ethylhexanol and the reaction time, a composition excluding 2-hydroxyethyl(2-ethylhexyl) p-phthalate and containing 96.7 wt% di(2-ethylhexyl) p-phthalate (DEHTP) was obtained using the same method as in Example 1. The remaining components in the composition, other than these two components, contain byproducts generated during the reaction process, and these byproducts contain dimer compounds in the amounts shown in Table 1 below.

[0120] Comparative Example 4

[0121] By controlling the input amount of 2-ethylhexanol and the reaction time, compositions comprising 21.5 wt% and 55.2 wt% of 2-hydroxyethyl(2-ethylhexyl) p-phthaloate and di(2-ethylhexyl) p-phthaloate (DEHTP), respectively, were obtained using the same method as in Example 1. The remaining components in the compositions, excluding these two components, contain byproducts generated during the reaction process, and these byproducts contain dimer compounds in the amounts shown in Table 1 below.

[0122]

[0123] Experiment 1: Evaluation of Sheet Performance

[0124] Using plasticizers from the Examples and Comparative Examples, test specimens were produced according to ASTM D638 under the following formulation and production conditions.

[0125] (1) Formula: 100 parts by weight of linear vinyl chloride polymer (LS100S), 50 parts by weight of plasticizer and 3 parts by weight of stabilizer (BZ-153T)

[0126] (2) Blending: Mix at 700 rpm at 98°C.

[0127] (3) Production of test samples: 1T to 3T sheets were produced by treating the samples with a roll mill at 160°C for 4 minutes, and with a press at 180°C for 2.5 minutes (low pressure) and 2 minutes (high pressure).

[0128] (4) Test Items

[0129] 1) Tensile strength: Using the ASTM D638 method, a 1T specimen was stretched at a crosshead speed of 200 mm / min using a UTM testing apparatus (manufacturer: Instron, model name: 4466), and the break point of the 1T specimen was measured. The tensile strength was calculated as follows.

[0130] Tensive strength (kgf / cm²) = Load value (kgf) / Thickness (cm) × Width (cm)

[0131] 2) Measurement of elongation: Using the ASTM D638 method, a 1T specimen was stretched at a crosshead speed of 200 mm / min using a UTM, and the break point of the 1T specimen was measured. The elongation was calculated as follows:

[0132] Elongation (%) = Length after elongation / Initial length × 100

[0133] 3) Measurement of tension and residual elongation: The measurement of tension and residual elongation is to measure the tensile strength and elongation remaining of the sample after heating to 100°C for 168 hours, and the measurement method is the same as the measurement method of tensile strength and elongation.

[0134] 4) Measurement of migration loss: Measurement was performed according to KSM-3156. Specifically, a test specimen with a thickness of 1 mm was obtained, and absorbent sheets that could move to both sides of the test specimen to absorb organic material displaced onto the surface of the test specimen were added. Then, a plate covering the entire test specimen was attached to it to apply a load of 1 kgf / cm². The test specimen was placed in a hot air circulating oven (80°C) for 72 hours, then removed from the oven and cooled to room temperature for 4 hours. Next, the plates and absorbent sheets attached to both sides of the test specimen were removed, and the weight of the specimen before and after placing it in the oven was measured to calculate the migration loss according to Equation 3 below.

[0135] Migration loss (%) = {[(Initial weight of test specimen at room temperature) – (Weight of test specimen after standing in oven)] / (Initial weight of test specimen at room temperature)} × 100

[0136] 5) Measurement of evaporation loss: After the produced sample is treated at 80°C for 72 hours, the weight of the sample is measured.

[0137] Volatile loss (wt%) = {[(Initial sample weight) – (Sample weight after treatment at 80°C for 72 hours)] / (Initial sample weight)} × 100

[0138] 6) Stress test (stress resistance): A 2 mm thick sample is bent and left to stand at 23°C for 168 hours. The degree of migration (leakage) is then observed on day 1, day 3, and day 7, and the results are described numerically. The closer the number is to 0, the better the stress resistance.

[0139] 7) Evaluation of carbonization properties: Samples with a thickness of 0.25 mm and a size of 40 cm x 1 cm were prepared and carbonized in a Mathis oven at 230°C at a rate of 5 mm / 10 seconds to measure the time at which black carbonization began. Excellent carbonization properties mean that carbonization started relatively late, while poor carbonization properties mean that carbonization started relatively early. The evaluation is expressed on a scale of 1 to 5 according to the degree of excellence, where 5 is excellent and 1 is poor.

[0140] 8) Measurement of absorption rate: The absorption rate was evaluated by measuring the time taken from mixing the resin and plasticizer with each other using a planetary mixer (Brabender, P600) until the torque of the mixer stabilized, under the conditions of 73°C and 60 rpm.

[0141] (5) Evaluation Results

[0142] The evaluation results of these projects are shown in Tables 2 and 3 below.

[0143]

[0144]

[0145] Referring to Tables 2 and 3 above, compared with Comparative Example 1, which is a typical phthalate-based plasticizer product, Examples 1 to 5 show superior results in terms of volatility loss, mechanical properties, stress resistance, and carbonization properties. In other words, this means that the plasticizer composition of the present invention, by using di(2-ethylhexyl) phthalate and 2-ethylhexyl(2-hydroxyethyl) phthalate together, exhibits improved stress resistance and mechanical properties without deteriorating typical physical properties. Generally, in compositions in which two components are mixed, the effect of the mixed composition tends to decrease in the effectiveness of each component. However, in the present invention, improvements in stress resistance and mechanical properties are achieved while maintaining physical properties at the same level as existing methods. Therefore, it can be demonstrated that the present invention achieves effects that cannot be predicted by the prior art.

[0146] Meanwhile, Comparative Example 2 was prepared from polyethylene terephthalate in a manner similar to that used in the embodiments of the present invention, except that a larger amount of 2-ethylhexanol was used and 2-hydroxyethyl(2-ethylhexyl) terephthalate was completely removed from the final composition through an additional separation process. The manufacturing process was more expensive than that of Examples 1 to 5, but the physical properties of the resulting plasticizer composition were similar to those of the plasticizer compositions of Examples 1 to 5. In particular, the results for anti-migration, stress resistance, and mechanical properties were inferior to those of the examples. Furthermore, the absorption rate was also inferior to that of the examples. From the above, it can be confirmed that the plasticizer composition of the present invention has a lower preparation cost than typical plasticizer compositions containing di(2-ethylhexyl) terephthalate recovered from polyethylene terephthalate, and also possesses excellent plasticizer function as is.

[0147] Meanwhile, Comparative Examples 3 and 4 were prepared from polyethylene terephthalate in a manner similar to that used in the embodiments of the present invention, and were plasticizer compositions having contents not within the content of 2-ethylhexyl (2-hydroxyethyl) terephthalate and / or dimer compounds according to the present invention by controlling the input amount of 2-ethylhexanol, reaction time, and purification process. The mechanical properties, migration loss, volatility loss, and stress resistance results were not as good as those of the embodiments. It can be confirmed from the above that when the plasticizer composition of the present invention, which limits the content of each compound to maximize improvement of various physical properties, such as mechanical properties, heat resistance, and migration resistance, is compared with the plasticizers of Comparative Examples 3 and 4 whose contents are not within the content of 2-ethylhexyl (2-hydroxyethyl) terephthalate and / or dimer compounds, the plasticizer composition of the present invention has excellent plasticizer function.

Claims

1. A plasticizer composition comprising 2-ethylhexyl (2-hydroxyethyl) phthalate and di(2-ethylhexyl) phthalate, wherein the content of 2-ethylhexyl (2-hydroxyethyl) phthalate is from 0.01 wt% to 20 wt% based on the total plasticizer composition.

2. The plasticizer composition of claim 1, wherein the content of 2-ethylhexyl (2-hydroxyethyl) phthalate is from 0.01 wt% to 15 wt%.

3. The plasticizer composition of claim 1, wherein the weight ratio between the 2-ethylhexyl (2-hydroxyethyl) phthalate and the di(2-ethylhexyl) phthalate is from 1:3 to 10000.

4. The plasticizer composition of claim 3, wherein the weight ratio between the 2-ethylhexyl (2-hydroxyethyl) phthalate and the di(2-ethylhexyl) phthalate is 1:5 to 1000.

5. The plasticizer composition of claim 1 further comprises one or more of the dimer compounds represented by formulas 1 to 3 below:

6. The plasticizer composition of claim 5, wherein the total content of the dimer compound in the composition is from 2 wt% to 20 wt%.

7. The plasticizer composition of claim 5, wherein the content of the dimer compound represented by Formula 1 above in the composition is from 0.01 wt% to 1 wt%.

8. The plasticizer composition of claim 5, wherein the content of the dimer compound represented by formula 3 above in the composition is from 0.3 wt% to 2.5 wt%.

9. The plasticizer composition of claim 5, wherein the weight ratio of the dimer compound to the 2-ethylhexyl (2-hydroxyethyl) phthalate in the composition is from 1:0.001 to 5.

10. The plasticizer composition of claim 5, wherein the weight ratio of the dimer compound to the di(2-ethylhexyl) phthalate in the composition is from 1:2.0 to 99.

0.

11. A method for preparing a plasticizer composition as claimed in any one of claims 1 to 10, the method comprising the step of mixing polyethylene terephthalate and 2-ethylhexanol in the presence of a catalyst to carry out a transesterification reaction, wherein the product of the transesterification reaction comprises 2-ethylhexyl (2-hydroxyethyl) terephthalate and di(2-ethylhexyl) terephthalate, wherein the polyethylene terephthalate is mixed in an amount of 80 wt% or less relative to the sum of the contents of polyethylene terephthalate and 2-ethylhexanol, wherein the polyethylene terephthalate comprises 50 wt% or more of discarded and recycled polyethylene terephthalate, and wherein the transesterification reaction is carried out at a reaction temperature of 120°C to 240°C for 10 minutes to 12 hours.

12. A resin composition comprising 100 parts by weight of resin and 5 to 150 parts by weight of a plasticizer composition as claimed in claim 1.

13. The resin composition of claim 12, wherein the resin is selected from one or more of the group consisting of: linear vinyl chloride polymers, paste vinyl chloride polymers, ethylene-vinyl acetate copolymers, ethylene polymers, propylene polymers, polyketones, polystyrene, polyurethanes, polylactic acid, natural rubber, and synthetic rubber.