• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention recommends a process for obtaining recycled material from multilayer PET (polyethylene terephthalate) containers of post-consumer and/or post-industrial origin, which can be recovered mechanically. The recycled material obtained by the proposed process is also an object of the present invention, which is made up of clean and crushed multilayer PET and a compatibilizing mixture. In this way, the compatibilizing mixture is formed by, at least, a thermoplastic matrix of polyolefinic character with a percentage between 10% and 45%, a reactive agent of vegetable origin in a percentage less than 7.5% of the total mixture and a tackifying agent based on rosin in a percentage less than 7.5% of the total mixture. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2823925A1
    申请号:ES202130117
    申请日:2021-02-15
    公开日:2021-05-10
    发明作者:Vargas Cristina Paola Pavón；Azor José Miguel Ferri；Cerda Joaquín Vilaplana；Bou Santiago Ferrándiz；Carrillo Luis Jesús Quiles；García Asunción Martínez；García Francisco José Parres；Amorós José Enrique Crespo；La Rosa Ramírez Harrison De；Madrigal María Dolores Samper；Carrasco Miguel Fernando Aldas；García Daniel García；Martínez Juan López
    申请人:Asociacion De Investig de la Industria Del Juguete Conexas Y Afijes Aiju；Universidad Politecnica de Valencia；
    IPC主号:
    专利说明:

    [0003] MULTILAYER PET CONTAINERS AND RECYCLED MATERIAL OBTAINED WITH THE SAME
    [0005] OBJECT OF THE INVENTION
    [0007] The present invention refers to a process for obtaining a recycled material from multilayer PET (polyethylene terephthalate) containers and a compatibilizing mixture formed by a thermoplastic polyolefinic matrix, a reactive agent of vegetable origin and a tackifying agent.
    [0009] The object of the invention is to obtain a recycled material from plastic waste from multilayer containers that contain a high content of PET to help reduce the use of chemical recycling and enable its recovery by mechanical recycling without degradation.
    [0011] BACKGROUND OF THE INVENTION
    [0013] Products made from multilayer PET are mainly used for food preservation. This requires that the container be made up of different materials, for example: PET in the outer layer to provide rigidity, EVOH (for its acronym Ethylene-Vinyl-Alcohol) for the intermediate layer that acts as a barrier to gases and LDPE ( Low Density Polyethylené) in the inner layer in contact with food.
    [0015] Each manufacturer applies different composition and layer specifications to obtain a multilayer PET according to the needs of the product. This combination of different materials in each layer prevents their mechanical recycling due to incompatibility problems between these materials, a mechanical recycling that is viable for non-multilayer PET containers.
    [0017] Therefore, the different fractions that make up multilayer PET containers must be separated (both in post-consumer and post-industrial containers) to avoid contamination in the general recycling of other polymers.
    [0018] On the other hand, the main problem that currently exists for the recycling of multilayer PET containers is that the recovery systems for post-consumer rigid containers in recycling plants are highly optimized to separate the materials into HDPE plastic fractions (due to their High Density Polyethylené) and PET. Consequently, after sorting, there is 15-20% multilayer fraction with high PET content (greater than 50%) that cannot be recycled and that ends up in landfill or incineration, since it causes contamination for the others. recycled polymer fractions. This problem is alarming, since only in Europe approximately 800,000 tonnes / year of this multilayer waste are generated.
    [0020] It should be noted that multilayer PET industrial waste (not from post-consumption) is currently not being recovered either in the company itself or by recyclers, due to the aforementioned incompatibility between the materials that make up the multilayer, giving rise to a high amount of waste material that cannot be recovered and is sent to landfill.
    [0022] For all the above, it is concluded that in the field of plastic waste there is an important technical problem derived from the lack of homogeneity of the plastic materials present. In fact, the heterogeneity of multilayer PET containers constitutes an impediment to their mechanical recycling, and it is currently necessary to address the chemical recycling of these materials with certain technical complexity and environmental impact. Thus, chemical recycling has the disadvantage of lower profitability, constituting a disposal system rather than a profitable recovery system.
    [0024] Thus, the present patent applicant detects the need to provide a process that allows obtaining a mechanically processable recycled material from multilayer PET containers.
    [0026] DESCRIPTION OF THE INVENTION
    [0028] The present invention recommends a process for obtaining a recycled material from containers that contain a high content of multilayer PET, where the containers are post-consumer waste and / or post-industrial waste.
    [0030] Post-consumer and post-industrial waste are multilayer, since they can be formed from three to eleven layers, being the presence of PET essential due to its barrier properties, which is why they are heterogeneous residues that contain, in addition to PET, other polymeric materials such as polypropylene, polyethylene, polyvinyl alcohol, polyamide, etc. according to the type of use for which the container is intended. All these materials are incompatible with each other when they are mechanically recycled by direct melting.
    [0032] Thus, the present invention proposes obtaining a recycled material - the result of the procedure that is detailed below - which can be recovered by means of mechanical recycling.
    [0034] Specifically, the waste involved in the process for obtaining recycled material is very specific, essentially being remains of film or sheets that contain multilayer PET in their composition predominantly used in food.
    [0036] In other words, the proposed procedure allows the recycling of plastic packaging waste from the yellow container, which is usually classified as various, and is not included in the categories of PET, HDPE or LDPE film. It is a material with a plurality of layers of different polymeric nature.
    [0038] The process of the invention comprises the following operational steps:
    [0040] - Cleaning of multilayer PET containers to eliminate odors and some impurities. In the cleaning stage a soapy solution is used. Preferably, but not limiting, the cleaning step is carried out by mechanical agitation and the multilayer PET containers being subjected to at least 60 ° C, and where the soapy solution is made up of an aqueous solution with 2% soap. . The mentioned soap is made up of 15% anionic surfactants and 5% non-ionic surfactants.
    [0041] - Separation of film and / or labels from multilayer PET containers, obtaining a clean multilayer PET material.
    [0042] - Grinding the clean multilayer PET material to a size of at least 1 mm.
    [0043] Preferably, in this crushing step, the clean and crushed multilayer PET material is obtained in the form of flakes smaller than 5 mm by 5 mm.
    [0044] - Mixing of the clean and crushed multilayer PET material, in a percentage of the 50% to 85% of the total mixture, with a compatibilizing mixture formed by at least one thermoplastic matrix of polyolefinic character with a percentage between 10% and 45% of the total mixture, a reactive agent of vegetable origin in a percentage less than 7.5% of the total mix and a tackifying agent based on rosin (modified pine resins) in a percentage less than 7.5% of the total mix.
    [0045] - Fusion of the mixture obtained in the previous stage by extrusion at a temperature between 200 ° C and 300 ° C to obtain a continuous filament
    [0047] Optionally, after the melting stage, the process of the invention includes a cutting stage by means of a pelletizer to section the continuous filament obtained in the melting stage, obtaining a thermoplastic pellet.
    [0049] Although it is true that said cutting stage can be replaced by a molding stage, in which the modeling of the continuous filament obtained in the melting stage intervenes by means of a nozzle of such configuration that it allows to directly obtain thermoplastic sheets and / or profiles. Said nozzle will be located at the head of the extruder that intervenes in the melting stage.
    [0051] By means of the procedure described, a recycled material is obtained that exhibits a very advantageous behavior, as concluded from the tests shown in the section on the preferred embodiment.
    [0053] Said recycled material is made up of clean and crushed multilayer PET material and a compatibilizing mixture made up of at least one thermoplastic matrix of polyolefinic character, a reactive agent of plant origin and a tackifying agent which is a natural product that improves bonding. among the elements that intervene in the recycled material and acts as a promoting agent.
    [0055] Specifically, the clean and crushed multilayer PET material intervenes in a percentage of 50% to 85% of the total mixture, while the compatibilizing mixture is formed by at least one thermoplastic matrix of polyolefinic character in a percentage between 10% and 45% of the total mixture, a reagent of vegetable origin in a percentage less than 7.5% of the total mixture and a tackifying agent based on rosin in a percentage less than 7.5% of the total mixture.
    [0056] The polyolefinic thermoplastic matrix is a polyolefin binder which is preferably integrated by polyethylene, polypropylene or a combination of both. Notwithstanding the foregoing, the polyolefinic thermoplastic matrix can also be made up of ionomer copolymers, ethylene vinyl acetate or polypropylene random copolymers.
    [0058] On the other hand, the reactive agent of vegetable origin that is part of the recycled material obtained according to the process object of the present invention can be an epoxidized soybean oil, an epoxidized linseed oil and / or a maleinized linseed oil. Advantageously, the use of a reactive agent of vegetable origin offers a lower environmental impact than others before petrochemical origin.
    [0060] In any case, the recycled material - which comes from multilayer PET containers of post-consumer and / or post-industrial origin - is obtained in a continuous filament format generated in the extrusion melt phase, which is easily moldable. or later transformable.
    [0062] Specifically, the recycled material can be in the form of thermoplastic pellets or pellets when it is passed through a pelletizer. Advantageously, the thermoplastic pellet format of the recycled material obtained enables its modification by any subsequent plastic transformation technique, being able to obtain very different plastic shapes: sheets, plates, injected, blown parts, etc.
    [0064] Thus, it is possible to obtain the recycled material of the present invention in a format of thermoplastic sheets or profiles when the extruder incorporates a nozzle with the appropriate configuration for this purpose.
    [0066] Consequently, the invention provides a solution to the problems associated with the processing of multilayer PET containers, which are highly heterogeneous, the recycling of which was not mechanically feasible until now. In this way, the process and material object of the present invention lead to the implementation of mechanical recycling, avoiding the massive use of chemical recycling, thus increasing the profitability of the recovery of multilayer PET.
    [0067] In short, the invention is proposed as a technological option with high added value in technical and environmental terms for the recovery of multilayer containers with a high content of PET in its composition, being a uniform material with a quality comparable to recycled polyolefins, suitable for use in the manufacture of traditional mechanical injection or extrusion products.
    [0069] DESCRIPTION OF THE DRAWINGS
    [0071] To complement the description that is going to be made below and in order to help a better understanding of the characteristics of the invention, according to some preferred examples of practical realization thereof, a set of drawings is attached as an integral part of said description. where, with an illustrative and non-limiting nature, the following has been represented:
    [0073] Figure 1.- Shows the calorimetric graphs obtained in the tests carried out for two preferred embodiments of recycled material obtained according to the process of the present invention.
    [0075] Figure 2.- Shows the results of the thermogravimetric analysis obtained for the tests carried out for two preferred embodiments of recycled material obtained according to the process of the present invention.
    [0077] PREFERRED EMBODIMENT OF THE INVENTION
    [0079] Below are two examples of the procedure for obtaining a recycled material from multilayer PET containers from post-consumer (test 1) and multilayer PET containers from post-industrial (test 2).
    [0081] TEST 1:
    [0083] In test 1, post-consumer multilayer PET containers are used. Specifically, the recycled material is prepared following the procedure described in the previous section, and where preferably two compounds or mixtures (mix A and mix B) were made from multilayer PET containers from post-consumption prepared according to the material. recycling object of the present invention.
    [0084] Thus, mixture A and mixture B are obtained from the use of a twin screw extruder in order to achieve good mixing and homogeneity of the recycled material obtained.
    [0086] The following table specifies the elements that make up mixture A and mixture B of test 1.
    [0091] To determine the optimum extrusion temperature, a thermal analysis was previously carried out by means of differential scanning calorimetry (DSC) tests of the clean multilayer PET containers. Based on which it is concluded that the melting peak of the different multilayer PET containers is between 247.5 and 249.5. In this sense, it was determined that the different samples of the present tests are extruded at 270 ° C at 30 rpm, previously drying the material at 60 ° C for 24 hours to eliminate residual moisture and thus avoid any hydrolytic degradation of the PET.
    [0093] Subsequently, a thermal characterization by DSC and a TGA thermogravimetric analysis of samples A and B prepared according to the method of the present invention are carried out. Figures 1 and 2 show the results of DSC and TGA for mixture A and mixture B of test 1. Specifically, in figure 1 the temperature expressed in ° C is represented on the abscissa axis while the ordinate axis is represents the thermal energy or heat flux expressed in mW. DSC detects any change that alters the heat flow to and from the sample due to glass transitions or melting of the material, among others. On the other hand, in Figure 2 the temperature expressed in ° C is represented on the abscissa axis, while the ordinate axis represents the mass loss, expressed in mg.
    [0095] As can be seen in Figure 1, the melting temperature of mixture A is is at 249.5 ° C and the melting temperature of Mix B is at 248.7 ° C.
    [0097] Likewise, a mechanical characterization of sample A and sample B is carried out, specifically by means of a tensile test (ISO 527, specimen 1BA, load cell 5 kN and speed of 5 mm / min) and a Charpy impact test (ISO 179 , notched, ISO 179-1 / 1eAb method).
    [0099] The results obtained in the mechanical characterization are included in the following table where it is observed that mixture A is more resistant, since the maximum resistance of 25.5 MPa and the elastic modulus of 941.5 MPa. Similarly, mixture A has a good elongation at break (63.6%) and the energy absorbed by said mixture in the Charpy impact test is 2.4 kJ / m2.
    [0101] On the other hand, mixture B shows a more ductile behavior, since the elongation at break reaches up to 361.8% and in the absorption of energy by Charpy impact it increases to 5.7 kJ / m2. On the contrary, the resistance decreases to 14.0 MPa and also the modulus to 143.0 MPa.
    [0103]
    [0106] From the results obtained in test 1, it is concluded that the resistance values for mixture A and mixture B oscillate between the values of a low-density polyethylene (LDPE) and a polypropylene (PP) copolymer of the random or random type.
    [0108] In addition, figure 2 allows to conclude that qualitatively curves are obtained that do not present discontinuities for sample A and sample B, that is, it can be concluded that the recycled material obtained from multilayer PET containers according to the process of the present invention presents a homogeneous character .
    [0110] TEST 2:
    [0112] In test 2 multilayer PET containers from post-industrial are used.
    [0113] Specifically, the recycled material is prepared following the procedure described in the description of the invention, and where preferably two compounds or mixtures (mix C and mix D) were made from multilayer PET containers from post-industrial prepared according to the recycled material object of the present invention.
    [0115] Likewise, in this test, mixture C and mixture D are obtained from the use of a twin screw extruder in order to achieve good mixing and homogeneity of the recycled material obtained.
    [0117] The following table specifies the elements that make up mixture C and mixture D of test 2.
    [0122] The mechanical characterization of sample C and sample D was carried out by means of a tensile test (ISO 527, specimen 1BA, load cell 5 kN and speed of 5 mm / min) and a Charpy impact test (ISO 179, with notch. ISO 179-1 / 1eAb method). The results obtained in the mechanical characterization are included in the following table.
    [0124]
    [0127] From the results obtained, it is concluded that mixture D is more resistant, since the maximum resistance of 35.5 MPa and the elastic modulus of 1126 MPa. Sample D also shows an excellent elongation at break (552%) and the energy absorbed in the Charpy impact test is 2.4 kJ / m2.
    [0130] On the other hand, mixture C shows a more ductile behavior, since the elongation at break reaches 567% and in the absorption of energy by Charpy impact it increases up to 5.7 kJ / m2.
    [0132] On the contrary, the strength of the mixture C decreases to 26.8 MPa and also the modulus to 814 MPa.
    [0134] From the results obtained in test 2, it is concluded that the resistance values for mixture C and mixture D also range between those of a low-density polyethylene (LDPE) and a polypropylene (PP) copolymer of the random or random type.
    权利要求:
    Claims (11)
    [1]
    1 Procedure for obtaining a recycled material from multilayer PET containers, which are from post-consumer and / or post-industrial, characterized in that it comprises the steps of:
    - Cleaning of multilayer PET containers using a soapy solution. - Separation of film and / or labels from multilayer PET containers, obtaining a clean multilayer PET material.
    - Grinding the clean multilayer PET material to a size of at least 1 mm. - Mixing of the clean and crushed multilayer PET material, in a percentage of 50% to 85% of the total mixture, with a compatibilizing mixture formed by at least one thermoplastic matrix of polyolefinic character in a percentage between 10% and the 45% of the total mixture, a reactive agent of vegetable origin in a percentage less than 7.5% of the total mixture and a tackifying agent based on rosin in a percentage less than 7.5% of the total mixture.
    - Fusion of the mixture obtained in the previous stage by extrusion at a temperature between 200 ° C and 300 ° C to obtain a continuous filament.
    [2]
    2. - Procedure for obtaining a recycled material from multilayer PET containers, according to claim 1, characterized in that the cleaning stage is carried out by mechanical stirring, at a temperature of at least 60 ° C and where the solution Soap is made up of an aqueous solution with 2% soap, the soap being made up of 15% anionic surfactants and 5% non-ionic surfactants.
    [3]
    3. - Procedure for obtaining a recycled material from multilayer PET containers, according to claim 1, characterized in that in the crushing stage the clean and crushed multilayer PET material is obtained in the form of flakes smaller than 5 mm by 5 mm.
    [4]
    4. - Procedure for obtaining a recycled material from multilayer PET containers, according to claim 1, characterized in that it includes a cutting stage by means of a pelletizer to section the continuous filament obtained in the melting stage, resulting in a thermoplastic pellet.
    [5]
    5. - Procedure for obtaining a recycled material from multilayer PET containers, according to claim 1, characterized in that it includes a molding stage in which the modeling of the continuous filament obtained in the melting stage intervenes by means of a configuration nozzle such that it allows to obtain thermoplastic sheets and / or profiles.
    [6]
    6. - Recycled material obtained from the process of any of the preceding claims, characterized in that it consists of clean and crushed multilayer PET material in a percentage of 50% to 85% of the total mixture and a compatibilizing mixture formed by at least one thermoplastic matrix of polyolefinic character with a percentage between 10% and 45% of the total mixture, a reactive agent of vegetable origin in a percentage less than 7.5% of the total mixture and a tackifying agent based on rosin in a percentage less than 7.5% of the total mix.
    [7]
    7. - Recycled material according to claim 6, characterized in that the polyolefinic thermoplastic matrix is made up of polyethylene and / or polypropylene.
    [8]
    8. - Recycled material according to claim 6, characterized in that the polyolefinic thermoplastic matrix is made up of ionomer copolymers, ethylene vinyl acetate or polypropylene random copolymers.
    [9]
    9. - Recycled material according to claim 6, characterized in that the reactive agent of vegetable origin is an epoxidized soybean oil, an epoxidized linseed oil and / or a maleinized linseed oil.
    [10]
    10. - Recycled material according to any of the claims from 6§ to 9§, characterized in that it is presented in a thermoplastic pellet format.
    [11]
    11. - Recycled material, according to any of the claims from 6§ to 9§, characterized in that it is presented in a format of thermoplastic sheets or profiles.
    1
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    同族专利:
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    引用文献:
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    KR20100031791A|2008-09-16|2010-03-25|최재영|The preparation method and devices of the recycling plastic products by the used vinyl compounds|
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    法律状态:
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    优先权:
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    ES202130117A|ES2823925B2|2021-02-15|2021-02-15|PROCEDURE FOR OBTAINING A RECYCLED MATERIAL FROM MULTILAYER PET CONTAINERS AND RECYCLED MATERIAL OBTAINED WITH THE SAME|ES202130117A| ES2823925B2|2021-02-15|2021-02-15|PROCEDURE FOR OBTAINING A RECYCLED MATERIAL FROM MULTILAYER PET CONTAINERS AND RECYCLED MATERIAL OBTAINED WITH THE SAME|
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