Process for preparing an element comprising polyethylene terephthalate with a view to its depolymerization

Abstract

The invention relates to a method for preparing a polyethylene terephthalate element, known as "PET", comprising at least one amorphization step in which the surface of the PET element is brought into contact with a plasma.

Description

Title of the invention: Process for preparing an element comprising polyethylene terephthalate with a view to its depolymerization Technical field of the invention

[0001] The present invention relates to the field of treatment methods, in particular of preparation for depolymerization thereof, of elements comprising polyethylene terephthalate. Prior art

[0002] Polyethylene terephthalate, or poly(ethylene terephthalate) is a very widely used polymer, particularly in the packaging and textile industries, or as a reinforcing element in tires. Its recycling is therefore a major issue.

[0003] To this end, different routes are possible: • So-called mechanical recycling allows PET objects to be remade from sorted, shredded and melted PET chips, but with inferior mechanical properties due to the presence of pollutants and the loss of molecular mass. PET from this recycling is therefore not suitable for reuse in applications for which high levels of performance are required; • So-called chemical recycling aims to return to the monomers (terephthalic acid, ethylene glycol) and therefore, after purification, allows the synthesis of a new polymer suitable for the intended applications. Among the recycling methods, we can distinguish methods using a solvent, with relatively severe operating conditions (pressure, temperature), therefore with an environmental impact and a high cost, and methods catalyzed by chemical effect (enzyme or other catalyst) or physical (microwave).

[0004] Enzymatic depolymerizations offer the advantage of being selective, and can therefore be carried out even in the presence of other plastic materials, and of requiring mild conditions, in water, at a pH generally ranging from 6 to 8 and a temperature of the order of 20 to 80°C. On the other hand, PET must be weakly crystalline so that the enzymes can adsorb correctly on the PET molecules.

[0005] Document WO2017 / 198786 describes a method comprising a step of amorphization of a PET element followed by a depolymerization step. The amorphization is carried out in a twin-screw extruder in which the PET is put under pressure and temperature. Although effective, this mode of operation may prove poorly suited to PET elements contaminated with compounds such as gum, which will degrade in the extruder and emit fumes. The twin-screw extruder is also an expensive piece of equipment.

[0006] This document also cites other possibilities for reducing the crystallinity of PET elements such as in a reactor, by atomization, by solubilization in a solvent, by plasma treatment, by atomic irradiation or by cryogenic mechanical attrition without further details.

[0007] Plasma treatment of PET elements, in particular reinforcement elements for tires, has already been implemented in the past with a view to improving the adhesion of the reinforcement to an elastomeric matrix. Document FR2996806 presents such a treatment whose problem is different because it involves treating the reinforcement at high speed, compatible with the calendering processes used in the tire industry, and on a very superficial layer, of the order of 0.5 μm to 1 μm, adhesion to the elastomeric matrix being a surface phenomenon.

[0008] Continuing its research, the applicant discovered that particular conditions of a plasma treatment made it possible to obtain a PET element particularly capable of being depolymerized, in particular in an enzymatic depolymerization step. Detailed description of the invention

[0009] The invention relates to a method for preparing a polyethylene terephthalate element, called "PET", for its depolymerization comprising at least one amorphization step in which the surface of the PET element is brought into contact with a plasma, followed by a step of depolymerization of the PET element, the apparent power of the plasma Papp=Pxd / (vxh), with P the power of the plasma in Watts, d the diameter of the plasma beam measured at the surface of the PET element in meters, v the speed of movement of the PET element relative to the plasma flow in meters / minute and h the distance between the plasma nozzle and the surface of the PET element in meters being such that 100xe < Papp < ​​330xe, with e the thickness of the PET element in millimeters. Definitions

[0010] The carbon-containing compounds mentioned in the description may be of fossil or bio-sourced origin. In the latter case, they may be, partially or totally, derived from biomass or obtained from renewable raw materials derived from biomass. This includes in particular polymers, plasticizers, fillers, etc.

[0011] Any interval of values ​​designated by the expression "between a and b" represents the range of values ​​from more than a to less than b (i.e., limits a and b excluded) while any interval of values ​​designated by the expression "from a to b" means the range of values ​​from a to b (i.e., including the strict limits a and b). Polyethylene terephthalate element

[0012] The polyethylene terephthalate element may be any element comprising polyethylene terephthalate. This element has a thickness e. Polyethylene terephthalate, or poly(ethylene terephthalate), hereinafter abbreviated to the acronym "PET", is a thermoplastic saturated polyester type polymer well known to those skilled in the art.

[0013] By thickness of the PET element is meant the smallest dimension measured in a section plane perpendicular to the main direction of said element, the main direction corresponding to the direction in which the element extends along its greatest length.

[0014] Thus, for a wire of circular section, the thickness e will correspond to the diameter of the wire. For a ribbon or a film, whose section is rectangular, the thickness e will correspond to the width of the rectangular section.

[0015] In one embodiment, the PET element is a monofilament, or elementary filament. Each monofilament preferably has a diameter less than or equal to 50 μm.

[0016] In one embodiment, the PET element comprises one or more multi-filament fibers.

[0017] A multifilament fiber is made up of several monofilaments or elementary filaments possibly intermingled with each other. Each fiber comprises between 50 and 2000 monofilaments.

[0018] In one variant, the PET element comprises one or more twists of multifilament fibers. The twist is obtained by twisting several overtwists, each overtwist being obtained by overtwisting a multifilament fiber.

[0019] In another variant, the PET element comprises an overtwist of a multifilament fiber.

[0020] In one embodiment, the PET element comprises a fabric of fibers. Such a fabric preferably comprises several twists of fibers assembled together by weaving using one or more weft threads. Alternatively, the fabric of fibers comprises two layers of fibers, the fibers of each layer extending in different directions from one layer to the other. In another alternative, the fabric of fibers comprises fibers assembled randomly and joined by friction, cohesion or adhesion (so-called "non-woven" fabric, or "non-woven" well known to those skilled in the art), the thickness of each fiber being less than 100 μm, preferably less than 50 μm.

[0021] In another embodiment, the PET element comprises a film. A film designates in particular any thin layer, the ratio of the thickness to the smallest of the other dimensions of which is less than 0.1. Preferably, the thickness of the film is preferably between 0.05 and 1 mm, more preferably between 0.1 and 0.7 mm. For example, film thicknesses of 0.20 to 0.60 mm have proven entirely satisfactory for most uses.

[0022] In one embodiment, the multifilament fiber, the fiber fabric, the non-woven fabric, the film or the monofilament is entirely made of a material chosen from polyethylene terephthalate and polyethylene naphthalate, preferably is entirely made of polyethylene terephthalate.

[0023] In another embodiment, the multifilament fiber, fiber fabric, non-woven fabric, film or monofilament comprises a first portion made of polyester and a second portion made of a material different from that of the first portion.

[0024] By different material is meant a material not identical to that of the first part. Thus, for example, a polyester of a different nature, or having a different crystallinity rate from that of the first part is a different material.

[0025] Preferably, the material of the first part is chosen from polyethylene terephthalate and polyethylene naphthalate, preferably is polyethylene terephthalate.

[0026] Preferably, the material of the second part is chosen from a polyester, for example polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polybutylene naphthalate (PBN), polypropylene terephthalate (PPT) or polypropylene naphthalate (PPN), a polyamide, for example an aromatic polyamide, a polyketone, a polyolefin, a cellulose, a natural fiber for example cotton or wool, or a mixture of these materials.

[0027] The material of the second part may also be another organic or non-organic component, such as a polyurethane, a silicone, a polyvinyl chloride, an acrylic resin, a phenolic resin, a reinforced or unreinforced rubber elastomer.

[0028] The material of the second part may consist of a formulation with organic or inorganic additives (plasticizers, crosslinking agent, protective agents). PET element amorphization step

[0029] The preparation method according to the invention comprises a step of amorphization of the PET element in which the surface of the PET element is brought into contact with a plasma.

[0030] A plasma makes it possible to generate, from a gas subjected to an electrical voltage, a thermal flux comprising molecules in the gaseous state, ions and electrons, the control of the electrical discharge making it possible to control the ionization of the gas and its temperature at the torch outlet. Advantageously, the plasma is of the cold plasma type. Such a plasma, also called non-equilibrium plasma, is such that the temperature comes from mainly from the movement of electrons. A cold plasma must be distinguished from a hot plasma, also called thermal plasma in which the electrons, but also the ions, give this plasma certain properties, notably thermal, different from those of the cold plasma.

[0031] Plasma is generated from a compressed gas. By compressed is meant that the gas is at a pressure higher than atmospheric pressure prior to plasma generation, the pressure to which the gas is compressed being a simple means of managing the atmospheric plasma flow rate. One skilled in the art can easily adjust the gas pressure depending on the plasma generation equipment and the desired plasma flow rate.

[0032] [Fig.l] [Fig.l] is a schematic representation of a method according to the invention. A PET element 1 is brought into contact with a plasma on each of its faces in two

[0033] devices 22a, 22b for generating a plasma flow. The treated PET element 3 then feeds an enzymatic depolymerization step 20 in order to produce an effluent comprising in particular terephthalic acid and / or ethylene glycol.

[0034] Each device 22a, 22b comprises a plasma torch 26 illustrated in detail in [Fig.2]. Each device 22a, 22b is intended to treat each surface of the PET element respectively.

[0035] For bringing the PET element into contact with the plasma, at least two plasma generating torches are preferably used, placed on either side of the PET element. Preferably, the torches are placed so as not to be opposite each other. The placement of the torches around the PET element is intended to ensure that the entire surface of the PET element is brought into contact with the plasma. The total number of torches can therefore be adjusted according to geometric constraints such as the shape of the PET element or the individual powers of each torch.

[0036] [Fig.2] [Fig.2] shows the device 22a for generating a flow of plasma, here a plasma torch 26 marketed by the company Plasmatreat GmbH. The device 22b is identical to the device 22a. The device 22a is powered by an alternating current of voltage less than 360 V and frequency between 15 and 25 kHz for a power consumption of 1000W.

[0037] The device 22a comprises means 34 for supplying gas to a chamber 36 for generating the plasma flow as well as means 38 for releasing the plasma generated in the chamber 36 in the form of a plasma flow 42, here a plasma jet. The device 22a also comprises means 44 for generating a rotating electric arc 46 in the chamber 36.

[0038] The supply means 34 comprise a conduit 48 for inlet of the gas into the chamber 36. The means 44 for generating the electric arc comprise an electrode 50. The outlet means 38 comprise an orifice 52 for outlet of the flow of plasma 42.

[0039] The PET element is brought into contact with the plasma at atmospheric pressure.

[0040] The use of a plasma at atmospheric pressure allows the installation of a relatively simple and inexpensive industrial installation unlike a process requiring the use of a plasma under reduced pressure associated with the installation of a depressurized chamber.

[0041] The stream 42 is obtained from a gas comprising at least one oxidizing component. By oxidizing component is meant any component capable of increasing the degree of oxidation of the chemical functions present in the polyester.

[0042] Advantageously, the oxidizing component is chosen from carbon dioxide (CO2), carbon monoxide (CO), hydrogen sulfide (H2S), carbon sulfide (CS2), dioxygen (O2), nitrogen (N2), chlorine (C12), ammonia (NH3) and a mixture of these components. Preferably, the oxidizing component is chosen from dioxygen (O2), nitrogen (N2) and a mixture of these components. More preferably, the oxidizing component is air.

[0043] Preferably, the plasma 42 is generated from air and nitrogen. By “generated from air and nitrogen” is meant that the gas used to generate the plasma comprises only air, optionally diluted with nitrogen, without the addition of any other additive.

[0044] By "air" is meant this term in its common meaning, that is to say a mixture of majority nitrogen, of the order of 78 mol%, of the order of 21% oxygen, the remainder being a mixture of gases such as for example argon and carbon dioxide. Preferably, the gas is a filtered gas.

[0045] Gas filtration allows the capture of possible unwanted bodies, such as fine oil droplets. A conventional practice is to use a one micrometer filter.

[0046] Preferably, the gas, preferably air optionally diluted with nitrogen, used for the generation of atmospheric plasma is free of organic compounds, or contains less than 1% by volume, preferably less than 0.5% by volume, very preferably less than 0.1% by volume.

[0047] Preferably, the gas, preferably air optionally diluted with nitrogen, used for the generation of the atmospheric plasma is free of halogenated compounds, or contains less than 1% by volume, preferably less than 0.5% by volume, very preferably less than 0.1% by volume.

[0048] Here, the flow 42 is obtained from a mixture of air and nitrogen at a flow rate ranging from 1000 1 / min to 3000 1 / min, preferably from 1500 1 / min to 2000 1 / min.

[0049] The orifice 52 is arranged opposite the element R to be treated, here opposite the surface SL

[0050] The orifice 52 is located at a constant distance h from the surface SI. Preferably, this distance ranges from 5 to 25 mm, preferably from 10 to 20 mm, more preferably from 10 to 15 mm. The greater the distance, the greater the power required to obtain a given reduction in crystallinity. Below 10 mm, the control of the amorphization of the PET element becomes very delicate and the necessary running speeds become very high. The risk of destroying the PET element becomes greater.

[0051] The element R is moved relative to the plasma flow at an average speed v less than or equal to 100 meters per minute, preferably 50 meters per minute and more preferably 30 meters per minute. The average speed v is equal to the ratio of the distance traveled by the plasma flow 42 relative to the surface to be exposed over a predetermined time taken to travel this distance. The movement of the flow relative to the element R may be rectilinear or curved or a mixture of the two. For example, the plasma flow may have a bous-trophedon movement relative to the element R so as to expose the entire surface SL

[0052] The plasma beam 42 has a diameter d.Thus, for a plasma power P (power consumed to produce the plasma), an average speed of movement of the PET element relative to the plasma flow v and a beam diameter d, the PET element receives an apparent power Papp equal to Papp = Pxd / (vxh), with P the plasma power in Watts, d the diameter of the plasma beam measured at the surface of the PET element in meters, v the speed of movement of the PET element relative to the plasma flow in meters / minute and h the distance between the plasma nozzle and the surface of the PET element in meters. The diameter d is measured from the width of the trace left after a first pass of the plasma at a distance h from a virgin PET plate.

[0053] It has been discovered that, in order to sufficiently lower the crystallinity of the PET element without risking damage to its structure, thus enabling good depolymerization performance to be obtained, the apparent power of the plasma must be such that 100xe < Papp < ​​330xe. If the apparent power is too high, the PET element is exposed too deeply and the risk of damaging it and reducing the depolymerization performance is increased. If the apparent power is too low, the lowering of the crystallinity is insufficient to enable satisfactory enzymatic depolymerization to be obtained.

[0054] By "sufficiently" is meant that the crystallinity of the PET element is, following the amorphization step, less than 25%, preferably less than 20%, and very preferably less than 15%. Indeed, such levels of crystallinity allow correct depolymerization of the PET, in particular by enzymatic means. Depolymerization step

[0055] Following the amorphization step, the PET element can therefore be treated in a depolymerization step.

[0056] Preferably, the depolymerization step is an enzymatic depolymerization step. During this step, the PET element is brought into contact with one or more enzymes allowing the depolymerization of the PET (depolymerases). Such an enzymatic depolymerization step is known to those skilled in the art, and described for example in document WO2017 / 198786.

[0057] The PET element treated under the conditions of the process according to the invention has an excellent capacity to be depolymerized, whether this depolymerization is carried out chemically or, preferably, enzymatically.

[0058] The depolymerization step is preferably carried out at a temperature ranging from 20 to 90°C in the liquid phase, at a pH ranging from 7 to 9. Preferably, the liquid phase is kept stirring in order to improve the contact between the PET and the depolymerase enzymes.

[0059] The invention also relates to a polyethylene terephthalate element capable of being obtained by a preparation process according to the invention. Beyond its crystallinity rate, it has appeared that such an element exhibits excellent degradability when used in a depolymerization process, in particular enzymatic. Examples Measurement of the crystallinity rate

[0060] The average crystallinity rate Ti of the PET element is measured by differential enthalpy analysis.

[0061] For this, the spectrum is acquired according to the ASTM D3418 standard. Then, the area Al, A2 of each crystallization and melting peak are measured respectively. The crystallinity rate T is given by the relation T=(A2-A1) / (AH*.G) in which AH* is the specific heat of fusion of the 100% crystalline polyester expressed in Jg 1 (AH*=145 J / g), and G the temperature gradient during the differential enthalpy analysis expressed in K. s1. Evaluation of amorphization treatment

[0062] Different PET elements are treated under the conditions presented in Table 1. The crystallinity of the PET element is measured after its treatment by differential enthalpy analysis. A crystallinity of less than 20% will allow good depolymerization of the element to be obtained in a depolymerization process such as that described in document WO2017 / 198786, namely a degradation of more than 40% by mass of the element after a treatment time of 7 hours. When the PET element is too damaged to undergo enzymatic treatment (burnt element, highly deformed), the crystallinity is not measured and the notation “-” is used. This element cannot be used in a depolymerization treatment.

[0063] [Tables 1] thickness •e power F torch / material distance BQ h 0 Spot d Speed ​​v W (i>WH 33O,e Crystalline 87 / 7? % 0.27 1000 0.815 4 25 27 10.7 89.1 23.6 0.27 1000 8.015 4 27.0 53.3 S9.1 17.4 0.27 1000 0.815 4 3. 27.0 §8.3 89À .16.5 0.27 1008 8.01 2.7 0 27.0 54.0 89.1 1 0.27 1000 0.01 2.7 3 27.0 30.0 89.1 - 0.38 1000 0.815 4 3- 330 38.3 125.4 15.8 8.38 1000 0.815 4 2? 3S.8 133.3 125.4 - 0.38 1800 0.815 4 5 as. 8 53.3 125.4 19.0 0.38 1000 8.015 4 15 38.0 17.8 3254 28.1 0.38 1800 0.815 4 25 33 0 10.7 225.-4 33.0 0.3® 1000 8.01 2.7 5 38.0 54.0 125.4 15.9 0.38 1800 0.01 Z, / 3 38.0 :30.0 125.4 11.5 ■' 0.01® 1000 0.01 2.7 100 1.8 Z, / 5.9 10.9 0.01® ICGOi 0.01 2 7 5Ü 1.8 5.4 5.9 8.3 c.ris w 0.01 2.7 '10 lS 27.8 5.9 -

Claims

Claims

1. A method of preparing a polyethylene terephthalate element, called "PET", for its depolymerization comprising at least one amorphization step in which the surface of the PET element is brought into contact with a plasma, followed by a step of depolymerization of the PET element, the apparent power of the plasma Papp=Pxd / (vxh), with P the power of the plasma in Watts, d the diameter of the plasma beam measured at the surface of the PET element in meters, v the speed of movement of the PET element relative to the plasma flow in meters / minute and h the distance between the plasma nozzle and the surface of the PET element in meters being such that 100xe < Papp < ​​330xe, with e the thickness of the PET element in millimeters.

2. Preparation process according to the preceding claim in which the plasma is generated from air and nitrogen.

3. Preparation process according to any one of the preceding claims in which the plasma flow rate ranges from 1000 1 / min to 3000 1 / min, preferably from 1500 1 / min to 2000 1 / min.

4. Preparation process according to any one of the preceding claims in which the distance h ranges from 5 to 25 mm, preferably from 10 to 20 mm, preferably from 10 to 15 mm.

5. Preparation process according to any one of the preceding claims in which the speed v is less than or equal to 100 meters per minute, preferably 50 meters per minute and more preferably 30 meters per minute.

6. A preparation process according to any one of the preceding claims wherein the depolymerization step is an enzymatic depolymerization step.

7. A preparation method according to any one of the preceding claims wherein the PET element is a monofilament, each monofilament preferably having a diameter less than or equal to 50 μm.

8. A preparation method according to any one of claims 1 to 7 wherein the PET element comprises one or more multifilament fibers.

9. A preparation method according to any one of claims 1 to 7 wherein the PET element comprises a fiber fabric.

10. Preparation process according to any one of claims 1 to 7

11.

12.

13. wherein the PET element comprises a film. Preparation process according to any one of claims 1 to 7 wherein the PET element comprises a non-woven fabric. A preparation method according to any preceding claim wherein the PET element comprises a first part made of polyester and a second part made of a material different from that of the first part. Preparation process according to the preceding claim in which the material of the second part is chosen from a polyester, a polyamide, a polyketone, a polyolefin, a cellulose, a natural fiber or a mixture of these materials.

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