Ethylenediheterothiophenic diacrylic conducting polymers, process for producing the same and use thereof for 3D printing

Abstract

Ethylenediheterothiophenic diacrylic conducting polymer having general formula (I): B-A (I) wherein: - B represents a polycation with statistical distribution of monomer units having general formula (II): wherein: - R1, equal to or different from each other, preferably equal to each other, represent a hydrogen atom, or are selected from C1-C24, preferably C1-C18, linear or branched, saturated or unsaturated alkyl groups, preferably represent a hydrogen atom; - - X represents an oxygen atom or a sulfur atom, preferably an oxygen atom; - T represents a group having general formula (III): wherein R2 represents a hydrogen atom, or is selected from C1-C18, preferably C1-C6, linear or branched, saturated or unsaturated alkyl groups, preferably represents a hydrogen atom or a methyl; - n is an integer ranging from 2 to 20, preferably ranging from 4 to 15; - m is an integer ranging from 1 to 48, preferably ranging from 10 to 45; - A represents one or more anions, optionally polymeric, capable of balancing the overall positive charge of the polycation having general formula (II); preferably represents one or more sulphonate anions having general formula (IV): R3-SO3 - (IV) wherein R3 is selected from C4-C30, preferably C4-C20, linear or branched, saturated or unsaturated, alkyl groups, optionally containing heteroatoms; optionally substituted aryl groups; optionally substituted heteroaryl groups; optionally substituted cycloalkyl groups; optionally substituted heterocyclic groups; or represents one or more sulphonated polyanions having general formula (V): wherein n' is an integer ranging from 15 to 250, preferably ranging from 50 to 200, y is a number ranging from 0.5 to 1, and x + y is equal to 1. Said ethylenediheterothiophenic diacrylic conducting polymer having general formula (I) can be advantageously used in the construction of electrodes for batteries, in particular aqueous or non-aqueous flow redox batteries. In addition, said ethylenediheterothiophenic diacrylic polymer having general formula (I) can be advantageously used in the construction of electrodes for hybrid or organic photovoltaic cells (or solar cells) or for perovskite-based photovoltaic cells (or solar cells). In addition, said ethylenediheterothiophenic diacrylic polymer having general formula (I) can be advantageously used in anticorrosive protection coatings for metal objects. Furthermore, said ethylenediheterothiophenic diacrylic conducting polymer has a good solubility in polymer resins usually used in 3D printing such as, for example, poly(ethylene glycol) diacrylate (PEGDA) and, consequently, can be advantageously used in compositions for 3D printing, in particular in 3D printing by photopolymerization.

Description

[0001] ETHYLENEDIHETEROTHIOPHENIC DIACRYLIC CONDUCTING POLYMERS, PROCESS FOR PRODUCING THE SAME AND USE THEREOF FOR 3D PRINTING

[0002] DESCRIPTION

[0003] The present invention relates to ethylenediheterothiophenic diacrylic conducting polymers.

[0004] More particularly, the present invention relates to an ethylenediheterothiophenic diacrylic conducting polymer having the specific general formula (I) reported below.

[0005] Said ethylenediheterothiophenic diacrylic conducting polymer having general formula (I) can be advantageously used in the construction of electrodes for batteries, in particular aqueous or non-aqueous flow redox batteries. In addition, said ethylenediheterothiophenic diacrylic polymer having general formula (I) can be advantageously used in the construction of electrodes for hybrid or organic photovoltaic cells (or solar cells) or for perovskite-based photovoltaic cells (or solar cells). In addition, said ethylenediheterothiophenic diacrylic polymer having general formula (I) can be advantageously used in anticorrosive protection coatings for metal objects. Furthermore, said ethylenediheterothiophenic diacrylic conducting polymer has a good solubility in polymer resins usually used in 3D printing such as, for example, poly(ethylene glycol) diacrylate (PEGDA) and, consequently, can be advantageously used in compositions for 3D printing, in particular in 3D printing by photopolymerization.

[0006] The present invention also relates to a process for preparing said ethylenediheterothiophenic diacrylic conducting polymer having the specific general formula (I) reported below.

[0007] Furthermore, the present invention relates to a 3D printing process for the production of manufactured articles comprising at least one ethylenediheterothiophenic diacrylic conducting polymer having the specific general formula (I) reported below.

[0008] The conducting polymers (PCs) are carbon-based materials, consisting of an alternation of single, double, or triple bonds, which allow the transport of charges. Several polymers belong to this category including, for example, poly(acetylene), poly(3,4-ethylenedioxythiophene) (PEDOT), poly(pyrrole) (PPy), poly(aniline) (PANI): said last three polymers are the most used and are also commercially available.

[0009] The conducting polymers (PCs) are used in different applications such as, for example, bioelectronics, flexible electronics, energy storage, as they can combine conducting properties and unique optoelectronic properties. Most of them, however, come in the form of infusible and insoluble powder materials, which are therefore difficult to process. Only in some cases, the coupling to polymeric counter-ions or the introduction of solubilizing chemical functionalities on the main chain makes them sufficiently processable for film deposition by “spin-coating” or “casting” techniques.

[0010] Of the three conducting polymers reported above, poly(3,4- ethylenedioxythiophene) (PEDOT) is the most widely used. It can be obtained through three types of polymerization: oxidative polymerization, electrochemical polymerization and transition metal-mediated polymerization.

[0011] Various oxidizing agents can be used in the oxidative polymerization. For example, iron(III) salts [e.g., iron (III) sulphate, iron (III) chloride, iron (III) p- toluenesulphonate] are preferred when oxidative polymerization is carried out in organic solvents and act both as efficient oxidizing agents and as a source of doping counter-ions (sulphate, chloride, -toluenesulphonate), while sodium peroxy di sulphate (Na2S20s) or potassium peroxydisulphate (K2S2O8), together with a catalytic amount of ferrous sulphate [Fe(SO)4], is used when polymerization is carried out in water. In the latter case, the two salts are coupled with the polymeric doping agent, i.e. poly(styrene sulphonate) (PSS) to obtain poly(3,4-ethylenedioxythiophene):polystyrene sulphonate (PEDOT :PSS).

[0012] Poly(3,4-ethylenedioxythiophene):polystyrene sulphonate (PEDOT :PSS) can also be obtained, as mentioned above, by electrochemical polymerization carried out on the surface of an electrode by applying an electric potential to a solution of 3, 4-ethylenedi oxythiophene (EDOT) and electrolyte: the oxidizing agent will therefore consist of the surface of the electrode. The first step provides for the oxidation of the monomer to a radical -cation, subsequently the generated radical-cation can couple with a second radical -cation or with a monomer, to produce a di-radical-cation from which, by losing two protons and consequent rearomatization, the dimer is obtained. This process continues until an insoluble polymer is formed which precipitates on the electrode. This technique is influenced by many factors, including the reaction solvent (aprotic solvents have to be used), the electrolyte, the material composing the electrode, but it has some advantages: for example, short polymerization times, use of low monomer concentrations, good control of the thickness of the film deposited on the electrode.

[0013] Finally, as mentioned above, poly(3,4-ethylenedioxythiophene):polystyrene sulphonate (PEDOT.PSS) can be obtained by transition metal-mediated polymerization. Said polymerization is used, in particular, to polymerize 3,4- ethylenedioxythiophene (EDOT) with side chains on the ethylene bridge, which are able to influence certain properties of the final polymer such as, for example, solubility, photochromism, packing.

[0014] Aqueous dispersions of poly(3,4-ethylenedioxythiophene)polystyrene sulphonate (PEDOT:PSS) are commercially available and are commonly used to formulate highly conducting electrodes usable in photovoltaic cells (or solar cells), organic light-emitting diodes (OLEDs), actuators, or in biomedical applications.

[0015] Dispersions in organic solvents are also commercially available such as, for example, nitromethane or propylene carbonate, of poly(3,4- ethylenedioxythiophene) (PEDOT) with polyethylene glycol (PEG)-based or terminal methacrylate functionalities, known under the trade name of Oligotron™.

[0016] Poly(3,4-ethylenedioxythiophenes) (PEDOT) with polyethylene glycol (PEG)-based or terminal methacrylate functionalities are described, for example, in patent US 7,361,728. Said patent reports the synthesis of poly(3,4- ethylenedioxythiophenes) (PEDOT) with polyethylene glycol (PEG)-based or terminal methacrylate functionalities through a glycidol ring opening reaction, which is a reaction by its nature poorly controlled and leads to poorly soluble compounds that, when used in subsequent processes, can have negative consequences from the point of view of some properties, such as strain to failure. Moreover, the use of some organic solvents instead of water limits the use of the aforementioned dispersions: for example, in the case of Oligotron™, the removal of propylene carbonate in order to use the pure compound is difficult to implement.

[0017] Another interesting aspect of poly(3,4-ethylenedioxythiophene) (PEDOT), in particular poly(3,4-ethylenedioxythiophene):polystyrene sulphonate (PEDOT:PSS), is the possibility of using it as an additive or main material in 3D printing processes.

[0018] 3D printing, also known as additive manufacturing (AM), refers to a group of techniques that allow an object to be manufactured layer by layer directly from a computer-aided design (CAD) model without specific tools for the parts and without material waste. 3D printing shows excellent process flexibility and greater control of geometry and thickness, thanks to layer-on-layer deposition, and also covers a wide spectrum of materials ranging from liquid solution, to powder, filament and laminate.

[0019] There are various 3D printing techniques but only the following three use polymers in the manufacturing process: inkjet printing, extrusion printing and photopolymerization printing.

[0020] Inkjet printing works with the same mechanism as the office inkjet printers: drops of a solution are first generated by a thermal, piezoelectric or electromagnetic stimulus and then expelled from a cartridge due to the pressure generated by the formation and collapse of micro-bubbles inside the nozzle. The inks used must not be viscous (viscosity values lower than 100 mPa*s), to ensure correct deposition and minimize the shear forces suffered by the material when it is expelled from the nozzle. Both water-based and organic solvent-based inks can be used but the formulation is rather challenging due to the low viscosity required, which involves the use of conducting polymer in low amounts. In the case of poly(3,4-ethylenedioxythiophene):polystyrene sulphonate (PEDOT :PSS), commercially available as an aqueous dispersion (Clevois®), the use thereof in inkjet printing processes is however facilitated.

[0021] Extrusion printing consists of layer-by-layer deposition of a material through a movable nozzle. It has two subcategories that differ in the way the polymer is extruded: fused deposition modeling (FDM) that uses a thermoplastic polymer in the form of a filament that is moved through a gear mechanism up to a hot end, wherein the polymer is fused and deposited on a surface and direct ink writing (DIW) that, instead, uses semi-finished polymers, in solutions or pastes, which are expelled from the nozzle thanks to the pressure applied on top of the tank, generally by a piston.

[0022] Both fused deposition modeling (FDM) and direct ink writing (DIW) require the use of polymers with a specific rheological behaviour, viscosity values lower than 104Pa*s for low shear rates (10'1x s'1) and 101Pa*s for high shear rates (102x s'1), in order to be printable and to maintain the desired shape after printing. In this case the conducting polymers must be combined with other thermoplastic polymers in the form of mixtures or copolymers: for example, in the case of poly(3 ,4-ethyl enedi oxythiophene) : pol y styrene sulphonate (PEDOT :P S S), copolymers have been made with polylactic acid (PLA) or caprolactone, capable of being processed with these techniques and having high printing performance.

[0023] Photopolymerization printing is a spatially controlled solidification of liquid monomers inside a tank. It is also divided into two subcategories: stereolithography (SLA) and digital light processing (DLP).

[0024] In stereolithography (SLA) the polymer resin is solidified in the upper part of the tank, point by point using a laser beam, and the object grows as it is immersed in the polymer resin. In digital light processing (DLP) a digital projector projects a beam of light with a 2D image of the object in question, the polymer resin then hardens plane by plane in the lower part of the tank and an elevator plate, after each exposure to the light beam, rises and repositions itself on the bottom in such a way as to have the right amount of volume of polymer resin to be polymerized.

[0025] Martinelli A. et al., in “ Materials Today Chemistry" (2022), Vol. 26, 101135. https: / / doi.Org / 10.1016 / j.mtchem.2022.101135, report an overview of the 3D printing of conducting polymers, including poly(3,4- ethylenedioxythiophene):poly(styrene sulphonate) (PEDOT:PSS). Among the disadvantages of using poly(3,4-ethylenedioxythiophene):poly(styrene sulphonate) (PEDOT:PSS) in polymer resins used in 3D printing, its low concentration, difficulty in printing and a decrease in conductivity are reported. The use of poly(3,4-ethylenedioxythiophene):polystyrene sulphonate (PEDOT:PSS) in 3D printing is also described, for example, by Yuk H. et al., in “Nature Communications” (2020), Vol. 11, 1604, https: / / doi.org / 10.1038 / s41467- 020-15316-7. The authors report a high-performance 3D printable conducting polymer ink based on poly(3,4-ethylenedioxythiophene):polystyrene sulphonate (PEDOT:PSS) for 3D printing of conducting polymers. In particular, they report a pasty conducting polymer ink based on cryogenic freezing of an aqueous solution of poly(3,4-ethylenedioxythiophene):polystyrene sulphonate (PEDOT:PSS) followed by lyophilization and controlled re-dispersion in a mixture of water and dimethylsulfoxide (DMSO). The aforementioned conducting polymer ink can also be used with other materials such as the insulating elastomers for multi-material 3D printing. 3D printing is carried out by extrusion and said conducting polymer ink is not suitable for 3D printing by photopolymerization.

[0026] Zhang L. G. et al., in “Materials Science & Engineering C” (2019), Vol. 99, p. 582-590, describe 3D printing by stereolithography (SLA) of a hydrogel obtained as follows: lyophilize an aqueous solution of poly(3,4- ethylenedioxythiophene): polystyrene sulphonate (PEDOT:PSS) obtaining a solid poly(3,4-ethylenedioxythiophene):polystyrene sulphonate (PEDOT:PSS); dissolve the solid poly(3,4-ethylenedioxythiophene):polystyrene sulphonate (PEDOT:PSS) in a mixture of distilled water and ethylene glycol; add polyethylene glycol diacrylate containing a photoinitiator. The obtained hydrogel contains poly(3,4-ethylenedioxythiophene):polystyrene sulphonate (PEDOT:PSS) in an amount lower than or equal to 0.91% and is not suitable for applications wherein good mechanical and structural strength is required.

[0027] However, the fact that conducting materials such as poly(3,4- ethylenedioxythiophene):polystyrene sulphonate (PEDOT:PSS) can present difficulties in printing (for example, in printing by fused deposition modeling (FDM), or poor solubility in the polymer resins usually used in 3D printing, in particular in 3D printing by photopolymerization, such as, for example, polyethylene glycol) diacrylate (PEGDA), makes the study of new conducting polymers, in particular of conducting polymers containing poly(3,4- ethylenedioxythiophene):poly(styrene sulphonate) (PEDOT:PSS), still of great interest.

[0028] The Applicant has therefore posed the problem of finding new conducting polymers, in particular conducting polymers containing poly(3,4- ethylenedioxythiophene):poly(styrene sulphonate) (PEDOT:PSS), usable in 3D printing, in particular in 3D printing by photopolymerization.

[0029] The Applicant has now found an ethyl enediheterothiophenic diacrylic conducting polymer having the specific general formula (I) reported below. Said ethylenediheterothiophenic diacrylic conducting polymer having general formula (I) can be advantageously used in the construction of electrodes for batteries, in particular aqueous or non-aqueous flow redox batteries. In addition, said ethylenediheterothiophenic diacrylic polymer having general formula (I) can be advantageously used in the construction of electrodes for hybrid or organic photovoltaic cells (or solar cells) or for perovskite-based photovoltaic cells (or solar cells). In addition, said ethylenediheterothiophenic diacrylic polymer having general formula (I) can be advantageously used in anticorrosive protection coatings for metai objects. Furthermore, said ethylenediheterothiophenic diacrylic conducting polymer has a good solubility in polymer resins usually used in 3D printing such as, for example, poly(ethylene glycol) diacrylate (PEGDA) and, consequently, can be advantageously used in compositions for 3D printing, in particular in 3D printing by photopolymerization.

[0030] The object of the present invention is therefore an ethylenediheterothiophenic diacrylic conducting polymer having general formula (I):

[0031] B-A (I) wherein:

[0032] B represents a polycation with statistical distribution of monomer units having general formula (II): wherein:

[0033] Ri, equal to or different from each other, preferably equal to each other, represent a hydrogen atom, or are selected from C1-C24, preferably Ci-Cis, linear or branched, saturated or unsaturated alkyl groups, preferably represent a hydrogen atom;

[0034] X represents an oxygen atom or a sulfur atom, preferably an oxygen atom;

[0035] T represents a group having general formula (III): wherein R2 represents a hydrogen atom, or is selected from Ci-Cis, preferably Ci -Ce, linear or branched, saturated or unsaturated alkyl groups, preferably represents a hydrogen atom or a methyl; n is an integer ranging from 2 to 20, preferably ranging from 4 to 15; m is an integer ranging from 1 to 48, preferably ranging from 10 to 45; A represents one or more anions, optionally polymeric, capable of balancing the overall positive charge of the polycation having general formula (II); preferably represents one or more sulphonate anions having general formula (IV): R3-SO3‘ (IV) wherein R3is selected from C4-C 0, preferably C4-C20, linear or branched, saturated or unsaturated alkyl groups, optionally containing heteroatoms; optionally substituted aryl groups; optionally substituted heteroaryl groups; optionally substituted cycloalkyl groups; optionally substituted heterocyclic groups; or represents one or more sulphonated polyanions having general formula (V): wherein n’ is an integer ranging from 15 to 250, preferably ranging from 50 to 200, y is a number ranging from 0.5 to 1, and x + y is equal to 1.

[0036] For the purpose of the present description and the following claims, the definitions of the numerical ranges always comprise the extreme values unless otherwise specified.

[0037] For the purpose of the present description and the following claims, the term “comprising” also includes the terms “which essentially consists of’ or “which consists of’.

[0038] For the purpose of the present description and the following claims, with the term “C1-C24 alkyl groups”, “Ci-Cis alkyl groups” and “C4-C 0 alkyl groups” are meant alkyl groups having from 1 to 24 carbon atoms, from 1 to 18 carbon atoms, and from 4 to 30 carbon atoms, respectively, linear or branched, saturated or unsaturated. Specific examples of C1-C24 alkyl groups, Ci-Cis alkyl groups and C4-C30alkyl groups are: methyl, ethyl, / / -propyl, / .w-propyl, / / -butyl, zso-butyl, tert-butyl, pentyl, ethyl-hexyl, hexyl, heptyl, / / -octyl, 2-ethyleptyl, 2-ethylhexyl,

[0039] 2-butenyl, 2-pentenyl, 2-ethyl-3-hexenyl, 3 -octenyl, l-methyl-4-h exenyl, 2 -butyl -

[0040] 3-hexenyl, lauryl, 4-hexyl-lauryl, cetyl, 2-butyl-cetyl, 4-hexyl-cetyl, stearyl, 2,4- dimethyl-stearyl, nonyl, decyl, dodecyl, 2-octyldodecyl, 2-ethyldodecyl, 2- butyloctyl, 2-hexyldecyl, 2-decyltetradecyl, 2-octyldodecyl.

[0041] For the purpose of the present description and the following claims, with the term “C4-C30 alkyl groups optionally containing heteroatoms” are meant alkyl groups having from 4 to 30 carbon atoms, linear or branched, saturated or unsaturated, in which at least one of the hydrogen atoms is substituted with a heteroatom selected from: halogens such as, for example, fluorine, chlorine, bromine, preferably fluorine; nitrogen; sulfur; oxygen. Specific examples of C4- C30 alkyl groups optionally containing heteroatoms are: perfluoropentyl, perfluoroctyl, perfluorodecyl, ethyl-2 -methoxy, propyl-3 -ethoxy, butyl-2- thiomethoxy, hexyl -4-amino, hexyl -3-N,N ’-dimethylamino, methyl -N,N’~ di octyl amino, 2-m ethyl -hexyl -4-amino .

[0042] For the purpose of the present description and the following claims, with the term “aryl groups” are meant aromatic carbocyclic groups containing from 6 to 60 carbon atoms. Said aryl groups can optionally be substituted with one or more groups, equal to or different from each other, selected from: halogen atoms such as, for example, fluorine, chlorine, bromine, preferably fluorine; hydroxyl groups; C1-C12 alkyl groups; C1-C12 alkoxy groups; C1-C12 thioalkoxy groups; C3-C24 trialkylsilyl groups; polyethyl eneoxylic groups; cyan groups; amino groups; Ci- C12 mono- or di-alkylamino groups; nitro groups. Specific examples of aryl groups are: phenyl, methylphenyl, trimethylphenyl, methoxyphenyl, hydroxyphenyl, phenyl oxyphenyl, fluorophenyl, pentafluorophenyl, chlorophenyl, bromophenyl, nitrophenyl, dimethylaminophenyl, naphthyl, phenylnaphthyl, phenanthrene, anthracene, phenoxy-phenyl, 4 -nitro-phenyl, 4-amino-phenyl, 3 -chloro-phenyl, trihydroxyphenyl .

[0043] For the purpose of the present description and the following claims, with the term “heteroaryl groups” are meant heterocyclic aromatic, penta- or hexa-atomic groups, also benzocondensed or heterobicyclic, containing from 4 to 60 carbon atoms and from 1 to 4 heteroatoms selected from nitrogen, oxygen, sulfur, silicon, selenium, phosphorus. Said heteroaryl groups can optionally be substituted with one or more groups, equal to or different from each other, selected from: halogen atoms such as, for example, fluorine, chlorine, bromine, preferably fluorine; hydroxyl groups; C1-C12 alkyl groups; C1-C12 alkoxy groups; C1-C12 thioalkoxy groups; C3-C24 trialkylsilyl groups; polyethyleneoxylic groups; cyan groups; amino groups; C1-C12 mono- or di-alkylamino groups; nitro groups. Specific examples of heteroaryl groups are: pyridine, methylpyridine, methoxypyridine, phenylpyridine, fluoropyridine, aminopyrimidine, pyrimidine, pyridazine, pyrazine, triazine, tetrazine, quinoline, quinoxaline, quinazoline, furan, thiophene, hexyl thiophene, bromothiophene, dibromothiophene, pyrrole, oxazole, thiazole, isooxazole, isothiazole, oxadiazole, tiadiazole, pyrazole, imidazole, triazole, tetrazole, indole, benzofuran, benzothiophene, benzooxazole, benzothiazole, benzooxadiazole, benzothiadiazole, benzopyrazole, benzimidazole, benzotriazole, triazolopyridine, triazolopyrimidine, coumarin.

[0044] For the purpose of the present description and the following claims, with the term “cycloalkyl groups” are meant cycloalkyl groups having from 5 to 60 carbon atoms. Said cycloalkyl groups can optionally be substituted with one or more groups, equal to or different from each other, selected from: halogen atoms such as, for example, fluorine, chlorine, bromine, preferably fluorine; hydroxyl groups; C1-C12 alkyl groups; C1-C12 alkoxy groups; C1-C12 thioalkoxy groups; C3-C24 trialkylsilyl groups; polyethyleneoxylic groups; cyan groups; amino groups; Ci- C12 mono- or di-alkylamino groups; nitro groups. Specific examples of cycloalkyl groups are: cyclopropyl, 2,2-difluorocyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, methoxycyclohexyl, fluorocyclohexyl, phenyl cyclohexyl, decalin, norbornyl, abietyl.

[0045] For the purpose of the present description and following claims, with the term “heterocyclic groups” are meant rings having from 3 to 12 atoms, saturated or unsaturated, containing at least one heteroatom selected from nitrogen, oxygen, sulfur, silicon, selenium, phosphorus, optionally condensed with other aromatic or non-aromatic rings. Said heterocyclic groups can optionally be substituted with one or more groups, equal to or different from each other, selected from: halogen atoms such as, for example, fluorine, chlorine, bromine, preferably fluorine; hydroxyl groups; C1-C12 alkyl groups; C1-C12 alkoxy groups; C1-C12 thioalkoxy groups; C3-C24 trialkylsilyl groups; polyethyleneoxylic groups; cyan groups; amino groups; C1-C12 mono- or di-alkylamino groups; nitro groups. Specific examples of heterocyclic groups are: pyrrolidine, methoxypyrrolidine, piperidine, fluoropiperidine, methylpiperidine, dihydropyridine, piperazine, morpholine, thiazine, indoline, phenylindoline, 2-ketoazetidine, diketopiperazine, tetrahydrofuran, tetrahy drothi ophene .

[0046] In accordance with a preferred embodiment of the present invention, said ethylenediheterothiophenic diacrylic conducting polymer has general formula (la):

[0047] B’-A’ (la) wherein:

[0048] B’ represents a polycation with statistical distribution of the monomer units having general formula (Ila): wherein n and m have the meanings reported above and R2 represents a hydrogen atom or a methyl;

[0049] A’ has the same meanings reported above for the substituent A.

[0050] In accordance with a further preferred embodiment of the present invention said ethylenediheterothiophenic diacrylic conducting polymer has general formula (lb):

[0051] B”-A” (lb) wherein:

[0052] B” represents a polycation with statistical distribution of the monomer units having general formula (lib) : wherein n and m have the meanings reported above;

[0053] A” represents one or more sulphonated anions having formula (IVb): or represents one or more sulphonated polyanions having general formula (Vb): wherein y is ranging from 0.5 to 1, x + y = 1 and n’ is ranging from 25 to 250, more preferably ranging from 100 to 200.

[0054] As reported above, a further object of the present invention is also a process for preparing an ethylenediheterothiophenic diacrylic conducting polymer having general formula (I).

[0055] Consequently, a further object of the present invention is a process for preparing an ethylenediheterothiophenic diacrylic conducting polymer having general formula (I):

[0056] B-A (I) wherein B and A have the same meanings reported above, comprising the following steps:

[0057] (a) reacting a compound having general formula (VI): wherein Ri and X have the same meanings reported above, with at least one 1,2-epoxyalkane, in the presence of / / -butyl lithium ( / / -BuLi) and of at least one anhydrous polar organic solvent, obtaining a compound having general formula (Via): wherein Ri and X have the same meanings reported above;

[0058] (b) reacting the compound having general formula (Via) with at least one halogenated acryloyl compound, in the presence of at least one anhydrous organic base, and of at least one anhydrous halogenated organic solvent, obtaining a compound having general formula (VIb): wherein Ri and X have the same meanings reported above;

[0059] (c) subjecting the compound having general formula (VIb) to oxidative polymerization, in the presence of an excess of the compound having general formula (VI), said step (c) being carried out:

[0060] (ci) in the presence of at least one polar aprotic organic solvent, of water, and of at least one oxidizing agent, obtaining an ethylenediheterothiophenic diacrylic conducting polymer having general formula (I); or

[0061] (C2) in the presence of water, of at least one oxidizing agent, of an iron (II) salt, and of at least one compound containing a sulphonated counterion, optionally polymeric, obtaining an ethylenediheterothiophenic diacrylic conducting polymer having general formula (I).

[0062] In accordance with a preferred embodiment of the present invention, in said step (a), said 1,2-epoxyalkane can be selected, for example, from 1,2-epoxy ethane, 1,2-epoxybutane, 1,2-epoxypropane, 1,2-epoxyhexane, or mixtures thereof, preferably 1,2-epoxybutane.

[0063] In accordance with a preferred embodiment of the present invention, in said step (a), said anhydrous polar organic solvent can be selected, for example, from tetrahydrofuran (THF), methyltetrahydrofuran, dioxane, or mixtures thereof, preferably tetrahydrofuran (THF).

[0064] In accordance with a preferred embodiment of the present invention, said step (a) can be carried out at a temperature ranging from 0°C to the boiling temperature of the used anhydrous polar organic solvent, preferably ranging from 20°C to 60°C.

[0065] In accordance with a preferred embodiment of the present invention, said step (a) can be carried out for a time ranging from 10 hours to 48 hours, preferably ranging from 15 hours to 20 hours.

[0066] In accordance with a preferred embodiment of the present invention, in said step (a), said compound having general formula (VI) can be used in said anhydrous polar organic solvent in an amount such as to have a molar concentration in said solvent ranging from 0.1 M to 0.5 M, preferably ranging from 0.25 M to 0.4 M.

[0067] In accordance with a preferred embodiment of the present invention, in said step (a) said compound having general formula (VI) and said / / -butyl lithium (n- BuLi) can be used in molar ratios ranging from 1.5: 1 to 1 : 1.6, preferably ranging from 1.1 : 1 to 1 : 1.2.

[0068] In accordance with a preferred embodiment of the present invention, in said step (a) said compound having general formula (VI) and said 1,2-epoxyalkane can be used in molar ratios ranging from 1.1 : 1 to 1 : 15, preferably ranging from 1 :2 to 1 :5. In accordance with a preferred embodiment of the present invention, in said step (b), said halogenated acryloyl compound can be selected, for example, from acryloyl chloride, methacryloyl chloride, or mixtures thereof, preferably acryloyl chloride.

[0069] In accordance with a preferred embodiment of the present invention, in said step (b), said anhydrous organic base can be selected, for example, from anhydrous trimethylamine, anhydrous triethylamine, anhydrous tributylamine, anhydrous 4- dimethylaminopyridine, or mixtures thereof, preferably anhydrous triethylamine, anhydrous 4-dimethylaminopyridine, or mixtures thereof.

[0070] In accordance with a preferred embodiment of the present invention, in said step (b), said anhydrous halogenated organic solvent can be selected, for example, from dichloromethane, ethylene dichloride, chloroform, carbon tetrachloride, preferably dichloromethane.

[0071] In accordance with a preferred embodiment of the present invention, said step (b) can be carried out at a temperature ranging from 10°C to 70°C, preferably ranging from 20°C to 60°C.

[0072] In accordance with a preferred embodiment of the present invention, said step (b) can be carried out for a time ranging from 5 hours to 24 hours, preferably ranging from 8 hours to 20 hours.

[0073] In accordance with a preferred embodiment of the present invention, in said step (b), said compound having general formula (Via) can be used in said anhydrous halogenated organic solvent in an amount such as to have a molar concentration in said solvent ranging from 0.05 M to 0.5 M, preferably ranging from 0.1 M to 0.3 M.

[0074] In accordance with a preferred embodiment of the present invention, in said step (b) said compound having general formula (Via) and said anhydrous organic base can be used in molar ratios ranging from 1 :2 to 1 : 15, preferably ranging from 1 :4 to 1 :7.

[0075] In accordance with a preferred embodiment of the present invention, in said step (c) said compound having general formula (VIb) and said compound having general formula (VI) can be used in molar ratios ranging from 1 :5 to 1 :50, preferably ranging from 1 : 10 to 1 :30. In accordance with a preferred embodiment of the present invention, in said step (ci), said polar aprotic organic solvent can be selected, for example, from acetonitrile, propionitrile, butyronitrile, or mixtures thereof, preferably acetonitrile.

[0076] In accordance with a preferred embodiment of the present invention, in said step (ci) said polar aprotic organic solvent and said water can be used in volume ratios (v / v) ranging from 95:5 to 99.9:0.1, preferably ranging from 97:3 to 99: 1.

[0077] In accordance with a preferred embodiment of the present invention, in said step (ci), said oxidizing agent can be selected, for example, from iron compounds such as, for example, iron (III) chloride, iron (III) sulphate, iron (III) p- toluenesulphonate, or mixtures thereof; preferably iron / 2-toluenesulphonate.

[0078] In accordance with a preferred embodiment of the present invention, in said step (ci), said compound having general formula (VIb) can be used in said polar aprotic organic solvent in an amount such as to have a molar concentration in said solvent ranging from 0.05 M to 0.5 M, preferably ranging from 0.1 M to 0.3 M.

[0079] In accordance with a preferred embodiment of the present invention, in said step (ci) said compound having general formula (VIb) and said oxidizing agent can be used in molar ratios ranging from 1 :40 to 1 :75, preferably ranging from 1 :45 to 1 :55.

[0080] In accordance with a preferred embodiment of the present invention, in said step (C2), said oxidizing agent can be selected, for example, from sodium, potassium, or cerium salts such as, for example, sodium peroxy di sulphate, potassium peroxydisulphate, cerium sulphate, cerium and ammonium sulphate, or mixtures thereof; preferably sodium peroxydisulphate, potassium peroxy di sulphate, or mixtures thereof.

[0081] In accordance with a preferred embodiment of the present invention, in said step (C2), said iron (II) salt can be selected, for example, from iron (II) sulphate, iron (II) chloride, iron (II) nitrate, or mixtures thereof; preferably iron (II) sulphate.

[0082] In accordance with a preferred embodiment of the present invention, in said step (C2), said compound containing a sulphonated counterion, optionally polymeric, can be selected, for example, from iron / 2-toluenesulphonate, sodium poly(styrene sulphonate) (Na-PSS), sodium camphorsulphonate, sodium benzenesulphonate, or mixtures thereof, preferably iron / 2-toluenesulphonate, sodium poly(styrene sulphonate) (Na-PSS), or mixtures thereof.

[0083] In accordance with a preferred embodiment of the present invention, in said step (C2) said compound having general formula (VIb) and said oxidizing agent can be used in molar ratios ranging from 1 : 10 to 1 :30, preferably ranging from 1 : 17 to 1 :24.

[0084] In accordance with a preferred embodiment of the present invention, in said step (C2) said compound having general formula (VIb) and said iron (II) salt can be used in molar ratios ranging from 1 :0.5 to 1 :3, preferably ranging from 1 :0.75 to 1 : 1.5.

[0085] In accordance with a preferred embodiment of the present invention, in said step (C2) said compound having general formula (VIb) and said compound containing a sulphonated counter-ion can be used in molar ratios ranging from 1 : 1 to 1 :5, preferably ranging from 1 : 1.2 to 1 :2.5.

[0086] In accordance with a preferred embodiment of the present invention, said step (ci) and said step (C2) can be carried out at a temperature ranging from 10°C to 80°C, preferably ranging from 20°C to 40°C.

[0087] In accordance with a preferred embodiment of the present invention, said step (ci) and said step (C2) can be carried out for a time ranging from 2 hours to 48 hours, preferably ranging from 8 hours to 25 hours.

[0088] As mentioned above, the present invention also relates to a 3D printing process for the production of manufactured articles comprising at least one ethylenediheterothiophenic polymer having general formula (I).

[0089] Consequently, the present invention also relates to a 3D printing process, by means of photopolymerization printing via digital light processing (DLP), for the production of manufactured articles comprising:

[0090] (ai) providing a polymer resin comprising:

[0091] (i) from 70% to 98% by weight, preferably from 75% by weight to 95% by weight, of at least one di(meth)acrylate of a polyethylene glycol (PEG) having a molecular weight ranging from 300 Daltons to 2000 Daltons, preferably ranging from 400 Daltons to 1000 Daltons;

[0092] (ii) from 2% by weight to 10% by weight, preferably from 2.5% by weight to 8% by weight, of at least one (meth)acrylate or (meth)acrylamide having general formula:

[0093] Ac -R wherein Ac is a (meth)acrylic or (meth)acrylamide residue and R is selected from C2 -C5 alkyl groups, linear or branched, C2-C5 hydroxyalkyl groups, linear or branched;

[0094] (iii) from 0.5% by weight to 8% by weight, preferably from 1% by weight to 6 % by weight, of at least one ethylenediheterothiophenic polymer having general formula (I);

[0095] (iv) from 0.5% by weight to 4% by weight, preferably from 1% by weight to 3% by weight, of at least one radical photoinitiator such as, for example, diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide (TPO), phenyl-di-( 2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), lithium phenyl-2,4,6-trimethylbenzoylphosphinate (LAP), preferably diphenyl (2,4,6-trimethylbenzoyl)phosphine oxide (TPO); the sum of (i) + (ii) + (iii) + (iv) being equal to 100;

[0096] (v) optionally, graphene or graphene oxide in an amount ranging from 0.05% by weight to 10% by weight, preferably ranging from 0.1% by weight to 8% by weight, per 100 parts by weight of (i) + (ii) + (iii) + (iv);

[0097] (bi) placing the reaction mixture obtained in step (ai) in a printing tank equipped with an aluminum platform and irradiating it with a light source emitting a wavelength ranging from 290 nm to 420 nm, for a time ranging from 5 minutes to 4 hours, preferably ranging from 8 minutes to 3 hours, at a temperature ranging from 20°C to 30°C, preferably at room temperature (25°C).

[0098] At the end of the polymerization, the three-dimensional manufactured article obtained is detached from the aluminum platform, washed with / .w-propanol to eliminate the uncrosslinked polymer resin residues and further crosslinked by crosslinking with ultraviolet radiation in order to remove any residues remaining inside the material.

[0099] It should be noted that the aforementioned 3D printing process can also be carried out by stereolithography (SLA).

[0100] As mentioned above, said ethylenediheterothiophenic diacrylate conducting polymer can be advantageously used in the construction of electrodes for batteries, in particular aqueous or non-aqueous flow redox batteries, in anti -corrosive coatings for metal objects.

[0101] Consequently, a further object of the present invention is an aqueous or nonaqueous flow redox battery, wherein the electrodes comprise at least one ethylenediheterothiophenic diacrylic conducting polymer having general formula (I).

[0102] Furthermore, as mentioned above, said ethylenediheterothiophenic diacrylic polymer having general formula (I) can be advantageously used in the construction of electrodes for hybrid or organic photovoltaic cells (or solar cells) or for perovskite-based photovoltaic cells (or solar cells).

[0103] Consequently, a further object of the present invention is a hybrid or organic photovoltaic cell (or solar cell) or a perovskite-based photovoltaic cell (or solar cell), wherein the electrodes comprise at least one ethylenediheterothiophenic diacrylic conducting polymer having general formula (I).

[0104] It should be noted that, compared to metal-based electrodes, electrodes comprising said ethylenediheterothiophenic diacrylic conducting polymer having general formula (I) have the advantage of not forming insulating oxides at the electrode-electrolyte interface. The polymeric nature of the electrode also gives the electrode itself a porous nature, thanks to the partial diffusion of the solvent of the electrolyte in the material that “swells” it, making the internal volume accessible to the electroactive components, whether they are electrically neutral or in ionic form, thus facilitating the redox processes underlying the operation of the battery. In addition, the ease of the manufacturing process by means of 3D printing techniques makes it possible to make electrodes with defined and particular morphologies.

[0105] Furthermore, as reported above, said ethylenediheterothiophenic diacrylic polymer having general formula (I) can be advantageously used in anticorrosive coatings for metal objects.

[0106] Consequently, a further object of the present invention is a metal object having an anticorrosive coating comprising at least one ethylenediheterothiophenic diacrylic conducting polymer having general formula (I).

[0107] In order to better understand the present invention and to put it into practice, some illustrative and non-limiting examples thereof are reported below.

[0108] EXAMPLE 1 (invention)

[0109] (a) Synthesis of l-(2,3-dihvdrothienol3,4-birL41dioxin-5-yl)butan-2-ol (1)

[0110] “a TA” = “at RT”

[0111] In a 100 ml two-necked flask, previously anhydrified, equipped with a magnetic stirrer, 50 ml of anhydrous tetrahydrofuran (dry THF) (Merck) and 2 g (14 mmol) of 3,4-ethylenedioxythiophene (EDOT) (Merck) were added: the whole was cooled to -78°C and, subsequently, 9.7 ml of a 1.6 M solution of n- butyl lithium (BuLi) in hexane (0.99 g, 15.5 mmol) (Merck) were added dropwise. The obtained reaction mixture was left, under stirring, at -78°C, for 15 minutes, subsequently cooled to 0°C in an ice-water bath and left at 0°C for 60 minutes. In the end, the temperature was brought back to -78°C and 10.14 g (140 mmol) of 1,2-epoxybutane were added and, after allowing the temperature to rise spontaneously to room temperature (25°C) (RT), the whole was left, under stirring, at said temperature, for 16 hours. Subsequently, the reaction mixture was quenched with 50 ml of a 1 M hydrochloric acid (HC1) solution (Merck), extracted three times with ethyl acetate (Merck) (3 x 75 ml) and the organic phase (obtained by combining the three organic phases) was anhydrified over magnesium sulphate (Merck). The obtained crude residue was purified by silica gel column chromatography elution (eluent hexane (Merck) / ethyl acetate (Merck) in a 7 / 3 v / v ratio) obtaining 2.62 g of l-(2,3-dihydrothieno[3,4-b][l,4]dioxin-5-yl)butan-2-ol (1) as a faint yellow liquid (yield = 87%)

[0112] (b) Synthesis of l-(2,3-dihydrothienol3,4-birL4]dioxin-5-yl)butan-2-yl acrylate (EDOT-A)

[0113] “TA” = “RT”

[0114] In a 200 ml two-neck flask, previously anhydrified, equipped with a magnetic stirrer, 100 ml of anhydrous di chloromethane (DCM) (Merck), 2 g (9.33 mmol) of l-(2,3-dihydrothieno[3,4-b][l,4] dioxin-5-yl)butan-2-ol (1) obtained in Example 1, 3.18 ml (23 mmol) of anhydrous tri ethylamine (EtsN dry) (Merck), 57 mg (0.47 mmol) of 4-dimethylaminopyridine (DMAP) (Merck) and 1.89 ml (23 mmol) of acryloyl chloride (Merck) were added: the reaction mixture obtained was left, under stirring, at room temperature (25°C), for 16 hours. The obtained crude reaction product was purified by silica gel column chromatography elution (eluent hexane (Merck) / ethyl acetate (Merck) in 95 / 5 v / v ratio) obtaining 1.5 g of l-(2,3-dihydrothieno[3,4-b][l,4]dioxin-5-yl)butan-2-yl acrylate (EDOT-A) (2) as a faint yellow liquid (yield = 60%). PLE 2 (invention) Synthesis of polv(3,4-ethylenedioxythiophene)diacrylate:polvstyrene sulphonate (PEDOTdA:PSS)

[0115] In a 100 ml single-neck flask equipped with a magnetic stirrer, 60 ml of water (H2O), 0.027 g (0.1 mmol) of l-(2,3-dihydrothieno[3,4-b][l,4] dioxin-5- yl)butan-2-yl acrylate (EDOT-A) (2) obtained in Example 1, 0.28 g (2 mmol) of 3, 4-ethylenedi oxythiophene (EDOT) (Merck), 2.81 g (19.7 mmol) of sodium polystyrene sulphonate (PSS) (NaPSS) (Merck), 0.57 g (2.1 mmol) of potassium peroxy di sulphate (K2S2O8) and 29.9 mg (0.2 mmol) of iron (II) sulphate (FeSO4) (Merck) were added: the reaction mixture obtained was left, under stirring, at room temperature (25°C), for 24 hours. The obtained crude reaction product was filtered with a 0.45 pm nylon filter, washed with 250 ml of an acetone (Merck) / methanol (Merck) solution (in a 1 : 1 v / v ratio) and subsequently with 150 ml of methanol (Merck) obtaining 0.8 g of poly(3,4-ethylenedioxythiophene)- diacrylate:polystyrene sulphonate (PEDOTdA:PSS).

[0116] EXAMPLE 3 (invention)

[0117] (c) / (ci) Synthesis of polv(3,4-ethylenedioxythiophene)diacrylate:tosylate (PEDOTdA:Tos)

[0118] In a 2-litre single-necked flask equipped with a magnetic stirrer, 1.37 litres of acetonitrile (Merck), 50 ml of water (ACN / H2O) and 72.7 g (107 mmol) of iron (III) -toluenesulphonate [Fe(III) -pTSA] (Merck) were added: the whole was kept under stirring, for 10 minutes, until complete solubilization. Subsequently, a solution of l-(2,3-dihydrothieno[3,4-b][l,4]dioxin-5-yl)butan-2-yl acrylate (EDOT-A) (2) (0.566 g; 2.1 mmol) obtained in Example 1, 3,4- ethylenedioxythiophene (EDOT) (Merck) (6 g; 42 mmol) in 50 ml of acetonitrile (Merck) were added: the reaction mixture obtained was left, under stirring, at room temperature (25°C), for 24 hours. In the end, the solvent was removed by evaporation under vacuum and the obtained crude residue was suspended in 150 ml of water, filtered with a 0.45 pm nylon filter and washed with 250 ml of methanol (Merck) obtaining 7.1 g of poly(3,4- ethylenedioxythiophene)diacrylate:tosylate (PEDOTdA:Tos).

[0119] EXAMPLE 4 (comparative)

[0120] Formulation of a “white” photo-resin i.e. without conducting polymer using polyethylene glycoDdiacrylate (PEGDA) l(Mn) 575 Daltonsl

[0121] For the purpose of the present example and examples 5-9 below, the percentages reported are to be understood as percentages by weight: the sum of the components being equal to 100.

[0122] In a 100 ml single-necked flask equipped with a magnetic stirrer, 1 g (2%) of diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide (TPO) (Merck) and 3.5 g (7%) of hydroxy ethyl methacrylate (HEMA) (Merck) were added: the whole was left, under stirring, at room temperature (25°C), for 30 minutes, until the diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide (TPO) was completely solubilized. Subsequently, 45.5 g (91%) of poly(ethylene glycol)-diacrylate (PEGDA) [number average molecular weight (Mn) 575 Daltons] (Merck) were added: the obtained solution was kept at room temperature (25°C) and homogenized by vigorous stirring (1000 rpm) for 30 minutes.

[0123] EXAMPLE 5 (comparative)

[0124] Formulation of a “white” photo-resin i.e without conducting polymer using poly(ethylene glycoDdiacrylate (PEGDA) (Mn) 700 Daltons

[0125] In a 100 ml single-necked flask equipped with a magnetic stirrer, 1 g (2%) of diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide (TPO) (Merck) and 3.5 g (7%) of hydroxy ethyl methacrylate (HEMA) (Merck) were added: the whole was left, under stirring, at room temperature (25°C), for 30 minutes, until the diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide (TPO) was completely solubilized. Subsequently, 45.5 g (91%) of poly(ethylene glycol)-diacrylate (PEGDA) [number average molecular weight (Mn) 700 Daltons] (Merck) were added: the obtained solution was kept at room temperature (25°C) and homogenized by vigorous stirring (1000 rpm) for 30 minutes.

[0126] EXAMPLE 6 (invention)

[0127] Formulation of a photo-resin with conducting polymer (PEDOTdA:Tos) at 3,5% by weight using poly(ethylene glycoDdiacrylate (PEGDA) (Mn) 575 Daltons

[0128] In a 100 ml single-necked flask equipped with a magnetic stirrer, 1 g (2%) of diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide (TPO) (Merck) and 3.5 g (7%) of hydroxy ethyl methacrylate (HEMA) (Merck) were added: the whole was left, under stirring, at room temperature (25°C), for 30 minutes, until the diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide (TPO) was completely solubilized. Subsequently, 43.75 g (87.5%) of polyethylene glycol)-diacrylate (PEGDA) [number average molecular weight (Mn) 700 Daltons] (Merck) and 1.75 g (3.5%) of poly(3,4-ethylenedioxythiophene)diacrylate:tosylate (PEDOTdA:Tos) obtained in Example 3 were added: the suspension obtained was kept at room temperature (25°C), sonicated for 30 minutes and subsequently homogenized by vigorous stirring (1000 rpm) for 16 hours.

[0129] EXAMPLE 7 (invention)

[0130] Formulation of a photo-resin with conducting polymer (PEDOTdA:Tos) at 3,5% by weight using poly(ethylene glycoDdiacrylate (PEGDA) (Mn) 700 Daltons

[0131] In a 100 ml single-necked flask equipped with a magnetic stirrer, 1 g (2%) of diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide (TPO) (Merck) and 3.5 g (7%) of hydroxy ethyl methacrylate (HEMA) (Merck) were added: the whole was left, under stirring, at room temperature (25°C), for 30 minutes, until the diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide (TPO) was completely solubilized. Subsequently, 43.75 g (87.5%) of polyethylene glycol)-diacrylate (PEGDA) [number average molecular weight (Mn) 700 Daltons] (Merck) and 1.75 g (3.5%) of poly(3,4-ethylenedioxythiophene)diacrylate:tosylate (PEDOTdA:Tos) obtained in Example 3 were added: the suspension obtained was kept at room temperature (25°C), sonicated for 30 minutes and subsequently homogenized by vigorous stirring (1000 rpm) for 16 hours.

[0132] EXAMPLE 8 (invention)

[0133] Formulation of a photo-resin with conducting polymer (PEDOTdA:Tos) at 5% by weight using poly(ethylene glycoDdiacrylate (PEGDA) (Mn) 575 Daltons

[0134] In a 100 ml single-necked flask equipped with a magnetic stirrer, 1 g (2%) of diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide (TPO) (Merck) and 3.5 g (7%) of hydroxy ethyl methacrylate (HEMA) (Merck) were added: the whole was left, under stirring, at room temperature (25°C), for 30 minutes, until the diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide (TPO) was completely solubilized. Subsequently, 43 g (86%) of poly(ethylene glycol)-diacrylate (PEGDA) [number average molecular weight (Mn) 575 Daltons] (Merck) and 2.5 g (5%) of poly(3,4-ethylenedioxythiophene)diacrylate:tosylate (PEDOTdA:Tos) obtained in Example 3 were added: the suspension obtained was kept at room temperature (25°C), sonicated for 30 minutes and subsequently homogenized by vigorous stirring (1000 rpm) for 16 hours.

[0135] EXAMPLE 9 (invention)

[0136] Formulation of a photo-resin with conducting polymer (PEDOTdA:Tos) at 5% by weight using poly(ethylene glycoDdiacrylate (PEGDA) (Mn) 700 Daltons

[0137] In a 100 ml single-necked flask equipped with a magnetic stirrer, 1 g (2%) of diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide (TPO) (Merck) and 3.5 g (7%) of hydroxy ethyl methacrylate (HEMA) (Merck) were added: the whole was left, under stirring, at room temperature (25°C), for 30 minutes, until the diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide (TPO) was completely solubilized. Subsequently, 43 g (86%) of poly(ethylene glycol)-diacrylate (PEGDA) [number average molecular weight (Mn) 700 Daltons] (Merck) and 2.5 g (5%) of poly(3,4-ethylenedioxythiophene)diacrylate:tosylate (PEDOTdA:Tos) obtained in Example 3 were added: the suspension obtained was kept at room temperature (25°C), sonicated for 30 minutes and subsequently homogenized by vigorous stirring (1000 rpm) for 16 hours.

[0138] EXAMPLE 10 (comparative)

[0139] 3D printing process using (“Digital Light Processing” - DLP)

[0140] 50 g of photo-resin obtained in Example 4 (Sample A) or in Example 5 (Sample B), were placed in a transparent printing tank composed of polymethyl methacrylate (PMMA) with the lower part covered with a fluorinated ethylene propylene film of a 3D printer (Sharebot Voyager). The printer was equipped with a light source (1920x1080 pixel LCD video projector) emitting at a wavelength of 405 nm with a brightness of 3000 ANSI lumens.

[0141] 4 objects having dumbbell shape geometry were created at the same time with the following dimensions: 50 mm long, 14 mm wide in the outer part and 7 mm wide in the central part, and 4 mm high.

[0142] Integrated within the 3D printer there was a mobile aluminium platform, on which, by moving it along the z dimension, the object was made to grow. At each layer, the platform was raised and lowered by 5 mm to mix the photo-resin: each layer had a height equal to 20 pm and the exposure time of each layer was equal to 1 second. The first layers were printed with longer exposure times to allow the object to adhere to the aluminium platform: the printing process took 25 minutes. EXAMPLE 11 (invention)

[0143] 3D printing process using (“Digital Light Processing” - DLP)

[0144] 50 g of photo-resin obtained in Example 6 (Sample C), or in Example 7 (Sample D), or in Example 8 (Sample E), or in Example 9 (Sample F), were placed in a transparent printing tank composed of polymethyl methacrylate (PMMA) with the lower part covered with a fluorinated ethylene propylene film of a 3D printer (Sharebot Voyager). The printer is equipped with a light source (1920x1080 pixel LCD video projector) emitting at a wavelength of 405 nm with a brightness of 3000 ANSI lumens.

[0145] 4 objects having dumbbell shape geometry were created at the same time with the following dimensions: 50 mm long, 14 mm wide in the outer part and 7 mm wide in the central part, and 4 mm high.

[0146] Integrated within the 3D printer there was a mobile aluminium platform, on which, by moving it along the z dimension, the object was made to grow. At each layer, the platform was raised and lowered by 5 mm to mix the photo-resin: each layer had a height of 20 pm and the exposure time of each layer was 5 seconds. The first layers were printed with longer exposure times to allow the object to adhere to the aluminium platform: the printing process took 25 minutes. EXAMPLE 12 (invention)

[0147] Tensile test for the measurement of elongation and characterization of the deformability of the samples obtained.

[0148] The mechanical tests were performed at room temperature using an MTS Insight 10 instrument (MTS System Corporation, USA) equipped with a 10 kN load cell. The object having dumbbell shape geometry printed in Example 10 (comparative) (Sample A) and in Example 11 (invention) (Sample D and Sample F) were hooked, on the long side, to the two clamps of the instrument and subsequently subjected to elongation until breakage, at a constant speed of the movable clamp of 2 mm / min. The displacements of the movable clamp and the measurements of the load cell were recorded with a sampling frequency of 20 Hz.

[0149] At the end of the tests, all the samples showed only elastic deformation before breakage.

Claims

CLAIMS1. Ethyl enediheterothiophenic diacrylic conducting polymer having general formula (I):B-A (I) wherein:B represents a polycation with statistical distribution of monomer units having general formula (II):Ri, equal to or different from each other, preferably equal to each other, represent a hydrogen atom, or are selected from C1-C24, preferably Ci-Cis, linear or branched, saturated or unsaturated alkyl groups, preferably represent a hydrogen atom;X represents an oxygen atom or a sulfur atom, preferably an oxygen atom;T represents a group having general formula (III):wherein R2 represents a hydrogen atom, or is selected from Ci -Cis, preferably Ci -Ce, linear or branched, saturated or unsaturated alkyl groups, preferably represents a hydrogen atom or a methyl;n is an integer ranging from 2 to 20, preferably ranging from 4 to 15; m is an integer ranging from 1 to 48, preferably ranging from 10 to 45; A represents one or more anions, optionally polymeric, capable of balancing the overall positive charge of the polycation having general formula (II); preferably represents one or more sulphonate anions having general formula(IV):R3-SO3- (IV) wherein R3is selected from C4- 0, preferably C4-C20, linear or branched, saturated or unsaturated, alkyl groups, optionally containing heteroatoms; optionally substituted aryl groups; optionally substituted heteroaryl groups; optionally substituted cycloalkyl groups; optionally substituted heterocyclic groups; or represents one or more sulphonated polyanions having general formula(V):wherein n’ is an integer ranging from 15 to 250, preferably ranging from 50 to 200, y is a number ranging from 0.5 to 1, and x + y is equal to 1.

2. Ethylenediheterothiophenic diacrylic conducting polymer according to claim 1 having general formula (la):B’-A’ (la) wherein:B’ represents a polycation with statistical distribution of the monomer units having general formula (Ila):wherein n and m have the meanings reported above in claim 1 and R2 represents a hydrogen atom or a methyl;A’ has the same meanings reported above in claim 1 for the substituent A.

3. Ethyl enediheterothiophenic diacrylic conducting polymer according to claim 1 having general formula (lb):B”-A” (lb) wherein:B” represents a polycation with statistical distribution of the monomer units having general formula (lib):wherein n and m have the meanings reported above in claim 1;A’ represents one or more sulphonate anions having formula (IVb):or one or more sulphonated polyanions having general formula (Vb):wherein y is ranging from 0.5 to 1, x + y = 1 and n’ is ranging from 25 to 250, more preferably ranging from 100 to 200.

4. Process for preparing an ethyl enediheterothiophenic diacrylic conducting polymer having general formula (I) according to claim 1 :B-A (I) wherein B and A have the same meanings reported above in claim 1, comprising the following steps:(a) reacting a compound having general formula (VI):wherein Ri and X have the same meanings reported above, with at least one 1,2-epoxyalkane, in the presence of / / -butyl lithium ( / / -BuLi) and of at least one anhydrous polar organic solvent, obtaining a compound having general formula (Via):wherein Ri and X have the same meanings reported above in claim 1;(b) reacting the compound having general formula (Via) with at least one halogenated acryloyl compound, in the presence of at least one anhydrous organic base, and of at least one anhydrous halogenated organic solvent,obtaining a compound having general formula (VIb):wherein Ri and X have the same meanings reported above in claim 1;(c) subjecting the compound having general formula (VIb) to oxidative polymerization, in the presence of an excess of the compound having general formula (VI), said step (c) being carried out:(ci) in the presence of at least one polar aprotic organic solvent, of water, and of at least one oxidizing agent obtaining an ethylenediheterothiophenic diacrylic conducting polymer having general formula (I); or(C2) in the presence of water, of at least one oxidizing agent, of an iron salt (II), and of at least one compound containing a sulphonated counterion, optionally polymeric, obtaining an ethylenediheterothiophenic diacrylic conducting polymer having general formula (I).

5. Process for preparing an ethylenediheterothiophenic diacrylic conducting polymer having general formula (I) according to claim 4, wherein: in said step (a), said 1,2-epoxyalkane is selected from 1,2-epoxy ethane, 1,2- epoxybutane, 1,2-epoxypropane, 1,2-epoxyalkane, or mixtures thereof, preferably 1,2- epoxybutane and / or in said step (a), said anhydrous polar organic solvent is selected from tetrahydrofuran (THF), methyltetrahydrofuran, dioxane, or mixtures thereof, preferably tetrahydrofuran (THF); and / or said step (a) is carried out at a temperature ranging from 0°C to the boiling temperature of the used polar organic solvent, preferably ranging from 20°C to 60°C; and / or said step (a) is carried out for a time ranging from 10 hours to 48 hours, preferably ranging from 15 hours to 20 hours; and / or in said step (a), said compound having general formula (VI) is used in said anhydrous polar organic solvent in an amount such as to have a molarconcentration in said solvent ranging from 0.1 M to 0.5 M, preferably ranging from 0.25 M to 0.4 M; and / or in said step (a) said compound having general formula (VI) and said n- butyl lithium (w-BuLi) are used in molar ratios ranging from 1.5: 1 to 1 : 1.6, preferably ranging from 1.1 :1 to 1 :1.2; and / or in said step (a) said compound having general formula (VI) and said 1,2- epoxyalkane are used in molar ratios ranging from 1.1 : 1 to 1 : 15, preferably ranging from 1 :2 to 1 :5.

6. Process for preparing an ethylenediheterothiophenic diacrylic conducting polymer having general formula (I) according to claim 4 or 5, wherein: in said step (b), said halogenated acrylic compound is selected from acryloyl chloride, methacryloyl chloride, or mixtures thereof, preferably acryloyl chloride; and / or in said step (b), said anhydrous organic base is selected from anhydrous trimethylamine, anhydrous triethylamine, anhydrous tributylamine, anhydrous 4-dimethylaminopyridine, or mixtures thereof, preferably anhydrous triethylamine, anhydrous 4-dimethylaminopyridine, or mixtures thereof; and / or in said step (b), said anhydrous halogenated organic solvent is selected from dichloromethane, ethylene dichloride, chloroform, carbon tetrachloride, preferably dichloromethane; and / or said step (b) is carried out at a temperature ranging from 10°C to 70°C, preferably ranging from 20°C to 60°C; and / or said step (b) is carried out for a time ranging from 5 hours to 24 hours, preferably ranging from 8 hours to 20 hours; and / or in said step (b), said compound having general formula (Via) is used in said anhydrous halogenated organic solvent in an amount such as to have a molar concentration in said solvent ranging from 0.05 M to 0.5 M, preferably ranging from 0.1 M to 0.3 M; and / or in said step (b) said compound having general formula (Via) and said anhydrous organic base are used in molar ratios ranging from 1 :2 to 1 : 15, preferably ranging from 1 :4 and 1 :7.

7. Process for preparing an ethylenediheterothiophenic diacrylic conducting polymer having general formula (I) according to any of claims from 4 to 6, wherein in said step (c) said compound having general formula (VIb) and said compound having general formula (VI) are used in molar ratios ranging from 1 :5 to 1 :50, preferably ranging from 1 : 10 to 1 :30.

8. Process for preparing an ethylenediheterothiophenic diacrylic conducting polymer having general formula (I) according to any one of claims 4 to 7, wherein: in said step (ci), said polar aprotic organic solvent is selected from acetonitrile, propionitrile, butyronitrile, or mixtures thereof, preferably acetonitrile; and / or in said step (ci) said polar aprotic organic solvent and said water are used in volume ratios (v / v) ranging from 95:5 to 99.9:0.1, preferably ranging from 97:3 to 99: 1; and / or in said step (ci), said oxidizing agent is selected from iron compounds such as iron (III) chloride, iron (III) sulphate, iron (III) / 2-toluenesulphonate, or mixtures thereof; preferably iron / 2-toluenesulphonate; and / or in said step (ci), said compound having general formula (VIb) is used in said polar aprotic organic solvent in such an amount as to have a molar concentration in said solvent ranging from 0.05 M to 0.5 M, preferably ranging from 0.1 M to 0.3 M; and / or in said step (ci) said compound having general formula (VIb) and said oxidizing agent are used in molar ratios ranging from 1 :40 to 1 :75, preferably ranging from 1 :45 to 1 :55.

9. Process for preparing an ethylenediheterothiophenic diacrylic conducting polymer having general formula (I) according to any one of claims 4 to 7, wherein: in said step (C2), said oxidizing agent is selected from sodium, potassium, or cerium salts such as sodium peroxydisulphate, potassium peroxy di sulphate, cerium sulphate, cerium and ammonium sulphate, or mixtures thereof; preferably sodium peroxydisulfate, potassium peroxy di sulfate, or mixtures thereof; and / or in said step (C2), said iron (II) salt is selected from iron (II) sulphate, iron (II) chloride, iron (II) nitrate, or mixtures thereof; preferably iron (II) sulphate;and / or in said step (C2), said compound containing a sulphonated counterion, optionally polymeric, is selected from iron / 2-toluenesulphonate, sodium poly(styrene sulphonate) (Na-PSS), sodium camphorsulphonate, sodium benzenesulphonate, or mixtures thereof, preferably -iron toluenesulfonate, poly(styrene sulfonate) (Na-PSS), or mixtures thereof; and / or in said step (C2) said compound having general formula (VIb) and said oxidizing agent are used in molar ratios ranging from 1 : 10 to 1 :30, preferably ranging from 1 : 17 to 1 :24; and / or in said step (C2) said compound having general formula (VIb) and said iron (II) salt are used in molar ratios ranging from 1 :0.5 to 1 :3, preferably ranging from 1 :0.75 to 1 : 1.5; and / or in said step (C2) said compound having general formula (VIb) and said compound containing a sulphonated counter-ion are used in molar ratios ranging from 1 : 1 to 1 :5, preferably ranging from 1 : 1.2 to 1 :2.5.

10. Process for preparing an ethyl enediheterothiophenic diacrylic conducting polymer having general formula (I) according to any one of claims from 4 to 9, wherein said step (ci) and said step (C2) are carried out: at a temperature ranging from 10°C to 80°C, preferably ranging from 20°C to 40°C; and / or for a time ranging from 2 hours to 48 hours, preferably ranging from 8 hours to25 hours.

11. 3D printing process, by photopolymerization printing via digital light processing (DLP), for the production of manufactured articles comprising:(ai) providing a polymer resin comprising:(i) from 70% to 98% by weight, preferably from 75% by weight to 95% by weight, of at least one di(meth)acrylate of a polyethylene glycol (PEG) having a molecular weight ranging from 300 Daltons to 2000 Daltons, preferably ranging from 400 Daltons to 1000 Daltons;(ii) from 2% by weight to 10% by weight, preferably from 2.5% by weight to 8% by weight, of at least one (meth)acrylate or (meth)acrylamide having general formula:Ac -R wherein Ac is a (meth)acrylic or (meth)acrylamide residue and R is selected from C2 -C5 alkyl groups, linear or branched, C2-C5 hydroxyalkyl groups, linear or branched;(iii) from 0.5% by weight to 8% by weight, preferably from 1% by weight to 6 % by weight, of at least one ethylenediheterothiophenic polymer having general formula (I);(iv) from 0.5% by weight to 4% by weight, preferably from 1% by weight to 3% by weight, of at least one radical photoinitiator such as, for example, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (TPO), phenyl -di-( 2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), lithium phenyl-2,4,6-trimethylbenzoylphosphinate (LAP), preferably diphenyl (2,4,6-trimethylbenzoyl)phosphine oxide (TPO); the sum of (i) + (ii) + (iii) + (iv) being equal to 100;(v) optionally, graphene or graphene oxide in an amount ranging from 0.05% by weight to 10% by weight, preferably ranging from 0.1% by weight to 8% by weight, per 100 parts by weight of (i) + (ii) + (iii) + (iv);(bi) placing the reaction mixture obtained in step (ai) in a printing tank equipped with an aluminum platform and irradiate it with a light source emitting a wavelength ranging from 290 nm to 420 nm, for a time ranging from 5 minutes to 4 hours, preferably ranging from 8 minutes to 3 hours, at a temperature ranging from 20°C to 30°C, preferably at room temperature (25°C).

12. Aqueous or non-aqueous flow redox battery, wherein the electrodes comprise at least one ethylenediheterothiophenic diacrylic conducting polymer having general formula (I) according to any one of claims 1 to 3.

13. A hybrid or organic photovoltaic cell (or solar cell) or a perovskite-based photovoltaic cell (or solar cell), wherein the electrodes comprise at least one ethylenediheterothiophenic diacrylic conducting polymer having general formula (I) according to any one of claims 1 to 3.

14. A metal object having an anticorrosive coating comprising at least oneethylenediheterothiophenic diacrylic conducting polymer having general formula(I) according to any one of claims 1 to 3.

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