Fullerene-functionalized (meth) acrylic polymer and preparation method thereof

Abstract

Fullerene-functionalized (meth) acrylic polymers of general formula (I): wherein:-x is a fraction of 0 to 0.89, preferably 0 to 0.6; -y is a fraction of from 0.01 to 0.99, preferably from 0.015 to 0.5; -z is a fraction from 0.1 to 0.99, preferably from 0.25 to 0.95; with the proviso that the sum of x + y + z equals 1; -p is an integer from 10 to 5000, preferably from 20 to 2500; -w is an integer from 50 to 250, preferably from 60 to 90, more preferably from 60, 70, 84; -n and m, equal to or different from each other, are integers from 1 to 12, preferably from 2 to 6; -R represents a hydrogen atom; or a linear or branched, saturated or unsaturated alkyl group, optionally containing heteroatoms, optionally substituted aryl group, optionally substituted heteroaryl group, optionally substituted cycloalkyl group, optionally substituted heterocyclic group, selected from C1-C20, preferably C1-C10, linear or branched, saturated or unsaturated alkyl groups, optionally containing heteroatoms, optionally substituted aryl group, optionally substituted heteroaryl group, optionally substituted cycloalkyl group, optionally substituted heterocyclic group; preferably hydrogen; -R1, equal to or different from each other, represent a hydrogen atom; or a linear or branched saturated or unsaturated alkyl group which is selected from C1-C20, preferably C1-C10, and optionally contains heteroatoms, preferably hydrogen or methyl; -R2 represents a hydrogen atom; or a linear or branched saturated or unsaturated alkyl group which is selected from C1-C20, preferably C1-C10, and optionally contains heteroatoms, preferably methyl, and is selected from C1-C20, preferably C1-C10, linear or branched, saturated or unsaturated alkyl groups optionally containing heteroatoms. Said fullerene-functionalized (meth) acrylic polymers of general formula (I) can be advantageously used as organic photovoltaic devices (or solar devices) (e.g., binary, ternary, quaternary organic photovoltaic cells (or solar cells), organic photovoltaic modules (or solar modules) with a simple or "tandem" structure) on rigid or flexible supports and an electron acceptor compound. In addition, the fullerene-functionalized (meth) acrylic polymer of general formula (I) can be advantageously used in perovskite-based photovoltaic cells (or solar cells) in electron transport layers (ETL). In addition, the fullerene-functionalized (meth) acrylic polymer of general formula (I) can be advantageously used for producing an organic thin film transistor (OTFT) or an organic field effect transistor (OFET). # imgabs0 #

Description

[0001] manual

[0002] The present invention relates to fullerene functionalized (meth)acrylic polymers.

[0003] More specifically, the present invention relates to fullerene functionalized (meth)acrylic polymers having the specific general formula (I) reported below.

[0004] The fullerene-functionalized (meth) acrylic polymers of general formula (I) can be advantageously used as electron acceptor compounds in organic photovoltaic devices (or solar devices) on rigid or flexible supports (e.g., binary, ternary, quaternary organic photovoltaic cells (or solar cells), organic photovoltaic modules (or solar modules) with simple or "tandem" structures). In addition, the fullerene-functionalized (meth) acrylic polymers of general formula (I) can be advantageously used in perovskite-based photovoltaic cells (or solar cells) in electron transport layers (ETLs). In addition, the fullerene-functionalized (meth) acrylic polymers of general formula (I) can be advantageously used in the production of organic thin film transistors (OTFTs) or organic field effect transistors (OFETs).

[0005] Another subject of the present invention is a process for preparing the fullerene-functionalized (meth)acrylic polymers of the general formula (I).

[0006] The present invention also relates to an organic photovoltaic device (or solar device) on a rigid support or a flexible support (e.g., an organic binary, ternary, quaternary solar cell, an organic photovoltaic module (or solar module) having a simple or "tandem" structure), which comprises at least one fullerene-functionalized (meth) acrylic polymer having a specific general formula (I).

[0007] The present invention also relates to a perovskite-based photovoltaic cell (or solar cell), wherein the electron transport layer (ETL) comprises at least one fullerene-functionalized (meth)acrylic polymer having the specific general formula (I).

[0008] The present invention also relates to an organic thin film transistor (OTFT) or an organic field effect transistor (OFET) comprising at least one fullerene-functionalized (meth)acrylic polymer having the specific general formula (I).

[0009] In the simplest mode of operation, an organic photovoltaic cell (or solar cell) is manufactured by introducing a thin photosensitive layer (about 100 nanometers) of a mixture of an electron acceptor compound and an electron donor compound between two electrodes, usually consisting of indium tin oxide (ITO) (anode) and aluminum (Al) (cathode), a structure known as "bulk heterojunction". In general, to manufacture a layer of this type, a solution of the two compounds is prepared, and subsequently, starting from said solution, a photoactive film is manufactured on the anode [indium tin oxide (ITO)] using a suitable deposition technique (such as "spin coating", "spray coating", "inkjet printing", etc.). Finally, the counter electrode [i.e. the aluminum cathode (Al)] is deposited on the dried film. Optionally, other additional layers can be introduced between the electrodes and the photoactive film, these layers being able to perform specific functions of an electrical, optical or mechanical nature.

[0010] Typically, in order to facilitate the passage of electron gaps (or holes) to the anode [indium tin oxide (ITO)] while blocking the transport of electrons, thereby improving the charge collection of the electrode and suppressing recombination phenomena, before starting to produce the photoactive film from a mixture of acceptor compounds and donor compounds as described above, a film is deposited starting from an aqueous suspension of PEDOT:PSS [poly(3,4-ethylenedioxythiophene) polystyrene sulfonate] using a suitable deposition technique (e.g. "spin coating", "spray coating", "inkjet printing", etc.).

[0011] In most cases, the electron acceptor compound is selected from C 60 , C 70 Fullerene derivatives, such as [6,6]-phenyl-C 61 -Butyric acid methyl ester (PC61BM), (6,6)-phenyl-C 71 - butyric acid methyl ester (PC71BM). However, the fullerene derivatives show poor solubility in solvents generally used for producing photovoltaic cells (or solar cells) and show a certain tendency to separate in the aforementioned photoactive layer.

[0012] One way to overcome the above disadvantages is to use C 60 Fullerene or C 70 Fullerenes are incorporated into polymer structures as reported in, for example, Giacalone F. et al., Chemical Reviews (2006), Vol. 106, No. 12, pp. 5136-5190; Giacalone F. et al., Advanced Materials (2010), Vol. 22, pp. 4220-4248.

[0013] Among the various attempts to introduce fullerenes into polymer structures, the use of acrylates and methacrylates as basic macromolecules must be mentioned. The synthetic strategies for the preparation of fullerene-containing (meth)acrylic polymers are in such an advanced state that a range of even highly complex structures can be synthesized by the most diverse polymerization techniques: from conventional free radical polymerization to the more complex atom transfer radical polymerization (ATRP). Thus, it is possible to obtain (meth)acrylic copolymers containing fullerenes of the random type, or (meth)acrylic copolymers containing fullerenes of the block type, which have high or low molecular weights and different polydispersity indices.

[0014] The class of (meth)acrylic acid copolymers containing side chain fullerenes is the most studied class. However, the most direct strategy (i.e., the synthesis of fullerene-functionalized (meth)acrylic acid monomers and their subsequent copolymerization by a free radical route) does not produce the desired polymers, as reported by, for example, Mehrotra S. et al., "Chemical Communications" (1997), pp. 463-464; Kirkwood K. et al., "Journal of Polymer Science Part A: Polymer Chemistry" (1997), Vol. 35, No. 15, pp. 3323-3325. The authors report that, in fact, during the polymerization, C 60 Fullerenes not only retard the polymerization process but also undergo multiple and random addition of free radical chains, producing complex polymer mixtures which cannot be regenerated and are even partially crosslinked, which makes the resulting polymers insoluble and therefore unusable for the purposes of the present invention.

[0015] C 60Other examples of fullerene functionalized poly(alkyl)methacrylates and poly(hydroxyalkyl)methacrylates are reported by Zheng J. et al., Polymer Bulletin (1997), Vol. 39, pp. 79-84; Lu ZH et al., Polymer Bulletin (1997), Vol. 39, pp. 661-667; Huang HL et al., Langmuir (2003), Vol. 19, pp. 5332-5335; Goh HW et al., Journal of Polymer Science Part A: Polymer Chemistry (2002), Vol. 40, No. 8, pp. 1157-1166. The authors report the synthesis of copolymers containing different amounts of alkyl methacrylates (e.g., methyl methacrylate, ethyl methacrylate, butyl methacrylate, or hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, or 6-hydroxyhexyl methacrylate). After the preparation of the above methacrylate copolymers, the hydroxyl groups are converted to azides in two steps to give azide polymers that can react with fullerenes to produce the desired C 60 Functionalized methacrylate copolymers, C 60 The fullerene content is 0.6 wt % to 7.4 wt %. C derived from alkyl methacrylate 60 -Fullerene functionalized methacrylate copolymers are soluble in tetrahydrofuran (THF), chlorobenzene or chloroform, whereas those derived from hydroxyalkyl methacrylates 60 -Fullerene functionalized methacrylate copolymers are soluble in dimethylformamide (DMF) or methanol.

[0016] However, it should be noted that a disadvantage of using the above-mentioned azide polymers is that unreacted azide groups subsequently give rise to crosslinking processes, which result in materials that are unstable over time, cannot be processed and are therefore unusable for the purposes of the present invention.

[0017] Sato H. et al., "Polymer Bulletin" (2015), Vol. 72, No. 11, pp. 904-909, reported the preparation of two different fullerene-containing methacrylate monomers by reaction of fullerenes with 4-azidobenzoyloxyethyl methacrylate or 4-azidobenzoyloxyethyl methacrylate. Interestingly, it was observed that subsequent anionic copolymerization experiments (with Grignard reagents) allowed the obtaining of monomers with low weight-average molecular weight (M w ) but contains up to 10.5 wt% C 60The free radical polymerization in the presence of α,α'-azobisisobutyronitrile (AIBN) as a free radical initiator did not occur, which further confirmed that C 60 The acrylic monomers cannot be free radically polymerized.

[0018] Ladelta V. et al., "Polymer Journal" (1998), Vol. 30, pp. 1265-1280 reported that a high C 60 Fullerene content (i.e. up to 41.4% by weight) of polymethyl methacrylate, which is obtained by reacting an azide-containing copolymer with C 60 The azide-containing copolymer is obtained by the reaction of fullerene in chlorobenzene. The azide-containing copolymer is derived from a random copolymer of 6-chlorohexyl methacrylate and methyl methacrylate, which is soluble in common organic solvents such as chloroform (CHCl 3 ), tetrahydrofuran (THF) and toluene. Size exclusion chromatography (SEC) showed that the polymethyl methacrylate in chloroform (CHCl 3 ) to form intramolecular and intermolecular aggregation, which may be due to C 60 The fullerene side groups interact strongly with each other, whereas they do not form these aggregates in tetrahydrofuran.

[0019] Tollan CM et al., "New Journal of Chemistry" (2008), Vol. 32, pp. 1373-1378 reported a method for synthesizing a C 60 A method for preparing acrylic polymers of fullerenes, the method first comprising synthesizing a monosubstituted C 60 Fullerene (i.e. monofullerene pyrrolidine) was then reacted with an acryloyl chloride / methyl acrylate copolymer. The amine groups of the monofullerene pyrrolidine reacted with the acyl chloride groups of the copolymer to form an amide bond. The method allowed the production of a 44 wt.% C 60 Acrylic polymers of fullerenes. However, as the authors point out, the presence of acyl chloride groups in the final polymers due to the incomplete substitution of the fullerene pyrrolidine reagent makes these materials less stable over time due to their high reactivity with moisture in the air. This drawback leads to a gradual crosslinking of the material, making it insoluble and therefore unusable for the purposes of the present invention, as the authors emphasize that for the polymer with the highest fullerene content (P4), it is already insoluble as soon as it is prepared.

[0020] Electron donor blocks containing poly-3-hexylthiophene (P3HT) and C 60 A method for the synthesis of block copolymers of electron acceptor blocks of fullerene-functionalized (meth)acrylic monomers.

[0021] For example, Lee JU et al., Journal of Materials Chemistry (2009), Vol. 19, pp. 1483-1489 reported a novel nanostructured carbon nanotube based on poly-3-hexylthiophene (P3HT) and C 60 Fullerene diblock copolymer (P3HT-bC 60 ). To this end, poly-3-hexylthiophene (P3HT) is first synthesized by Grignard metathesis polymerization, and then methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) are copolymerized using terminal functionalized poly-3-hexylthiophene (P3HT) (for example, functionalized with bromine) as an atom transfer radical polymerization (ATRP) macroinitiator to obtain a diblock copolymer [P3HT-bP(MMA-r-HEMA)]. Subsequently, a fullerene derivative (for example, [6,6]-phenyl-C 61 -methyl butyrate (PC61BM)) was chemically bonded to the second HEMA block of the diblock copolymer to obtain a diblock copolymer (P3HT-bC 60 ). Containing the diblock copolymer (P3HT-bC 60 ) are said to show nanoscale phase separation and overall fluorescence "quenching".

[0022] Yang C. et al., Journal of Materials Chemistry (2009), Vol. 19, pp. 5416-5423, reported the synthesis of diblock copolymers [P3HT-bP (styrene)] by a combination of living polymerization and subsequent cycloaddition. x Acrylate y )-C 60 ]. The aforementioned diblock copolymer (as is or in film form) is said to exhibit a nanofibrous structure and when used in an amount of 5 wt % in a mixture of P3HT:PCBM, is said to improve the performance of photovoltaic devices by 35%.

[0023] Li J. et al., Journal of Materials Chemistry (2009), Vol. 19, pp. 5416-5423 reported that 60 Fullerenes (measured by UV-vis, with an average of up to 78 C per chain) 60 To this end, pure C 60The functionalized monoalkynyl fullerene is prepared by starting with fullerene. Subsequently, methyl methacrylate and 6-azido-hexyl methacrylate are randomly copolymerized by RAFT polymerization ("reversible addition fragmentation chain transfer polymerization") to obtain a copolymer, which is reacted with the functionalized monoalkynyl-fullerene by a copper-catalyzed "click" reaction to obtain the aforementioned polymethacrylate. The aforementioned polymethacrylate containing a large amount of C 60 Fullerene polymethacrylates show interchain “self-aggregation” behavior both in solution and in silicon, which is strongly dependent on the C 60 The amount of fullerenes.

[0024] Biglova YN et al., "Russian Journal of Physical Chemistry B" (2017), Vol. 11, No. 2, pp. 324-329 reported the copolymerization and homopolymerization of fullerenes containing acrylates with vinyl monomers. The fullerene-containing copolymers are said to be easily soluble in common organic solvents, while the fullerene-containing homopolymers cannot be characterized due to high crosslinking.

[0025] J. et al., “Journal of Applied Polymer Science” (2018), Vol. 135, No. 10, 45916 reported a self-healing polymeric material composed of poly(lauryl methacrylate) having an anthracene unit in the side chain, C 60 Fullerene and [6,6]-phenyl-C 61 -Methyl ester of butyric acid (PC61BM) is covalently but reversibly bonded to the anthracene unit. 60 The bonds formed between fullerenes by cycloaddition [4+2] are reversible, breaking and reforming at 40° C.-60° C. The use of differently substituted anthracene monomers allows tuning of the reactivity and resulting mechanical properties.

[0026] However, although the fullerene derivatives known in the art have excellent chemical and physical properties for their application in organic photovoltaic devices (or solar devices), they may also involve various technical problems (for example, in terms of their performance) during the preparation process of the photovoltaic device (or solar device) or when used in the photovoltaic device (or solar device).

[0027] As mentioned above, a major disadvantage is their low solubility in non-toxic solvents and their high solubility in toxic solvents (e.g., halogenated solvents or carbon disulfide (CS 2 In addition, in order to obtain good results in the performance of photovoltaic devices (or solar devices), a large amount of fullerene derivatives must be dispersed in the photoactive layer.

[0028] Furthermore, due to the large surface area of ​​π-π, fullerene derivatives have a tendency to segregate within the photoactive layer even in the solid state, resulting in a drastic decrease in the efficiency of photovoltaic devices (or solar devices) because the formation of crystallites of fullerene derivatives limits the photophysical processes under their operation.

[0029] Furthermore, the methods for preparing fullerene derivatives are usually complicated multi-step processes that are not suitable for industrial processes. Furthermore, the methods usually use halogenated solvents, which are toxic as mentioned above and are therefore undesirable for industrial processes.

[0030] The Applicant therefore solved the problem of finding new fullerene derivatives and processes for their preparation which are able to overcome the above-mentioned disadvantages.

[0031] The Applicant has now discovered fullerene-functionalized (meth)acrylic polymers of the specific general formula (I) reported below and processes for their preparation which overcome the aforementioned disadvantages.

[0032] The fullerene-functionalized (meth) acrylic polymer of general formula (I) can be advantageously used as an electron acceptor compound in an organic photovoltaic device (or solar device) on a rigid support or a flexible support (selected from, for example, binary, ternary, quaternary organic photovoltaic cells (or solar cells), organic photovoltaic modules (or solar modules) with a simple or "tandem" structure). In addition, the fullerene-functionalized (meth) acrylic polymer of general formula (I) can be advantageously used in perovskite-based photovoltaic cells (or solar cells) in an electron transport layer (ETL). In addition, the fullerene-functionalized (meth) acrylic polymer of general formula (I) can be advantageously used in the production of organic thin film transistors (OTFTs) or organic field effect transistors (OFETs).

[0033] Furthermore, the fullerene functionalized (meth) acrylic polymer of formula (I) has good solubility, which ensures that the synthesis process does not form cross-linked materials. In particular, the fullerene functionalized (meth) acrylic polymer of formula (I) has good solubility (i.e., solubility equal to 30 mg / ml-40 mg / ml) in tetrahydrofuran (THF), methyltetrahydrofuran (Me-THF), dimethyl sulfoxide (DMSO), dioxane, i.e., in solvents that are considered to be environmentally "green". In this regard, it should be noted that the vast majority of fullerene derivatives and C 60Fullerenes exhibit almost zero solubility in this type of solvents [i.e., tetrahydrofuran (THF), methyltetrahydrofuran (Me-THF), dimethyl sulfoxide (DMSO), dioxane], and therefore the fullerene-functionalized (meth)acrylic polymers of formula (I) can be used in photovoltaic devices or conventionally by reacting with conventionally deposited C 60 or C 70 The layers can be deposited from solutions in chlorobenzene or xylene in the same manner as the fullerene derivatives, or in an unconventional manner, i.e. from solutions in solvents such as tetrahydrofuran (THF), methyltetrahydrofuran (Me-THF), dimethyl sulfoxide (DMSO), dioxane, making it possible, for example, to deposit the layers with perovskite precursors such as lead iodide (PbI 2 ) and methylammonium iodide (MeNH 3 I)) Co-deposition.

[0034] Furthermore, the fullerene-functionalized (meth) acrylic polymer of the general formula (I) can be obtained by a one-step process in the presence of a non-halogenated solvent. Furthermore, it should be noted that the process allows obtaining fullerene-functionalized (meth) acrylic polymers of the general formula (I) containing varying amounts of fullerene and hydroxyl (-OH) groups, which are therefore capable of producing layers that are compatible with both the hydrophobic and hydrophilic layers typically found in organic photovoltaic devices (or solar devices) or in perovskite-based photovoltaic cells (or solar cells).

[0035] The object of the present invention is therefore fullerene-functionalized (meth)acrylic polymers having the general formula (I):

[0036]

[0037] in:

[0038] - x is a fraction from 0 to 0.89, preferably from 0 to 0.6;

[0039] -y is a fraction from 0.01 to 0.9, preferably from 0.015 to 0.5;

[0040] - z is a fraction from 0.1 to 0.99, preferably from 0.25 to 0.95;

[0041] -The premise is that the sum of x+y+z is equal to 1;

[0042] - p is an integer from 10 to 5000, preferably from 20 to 2500;

[0043] -w is an integer from 50 to 250, preferably from 60 to 90, more preferably 60, 70, 84;

[0044] - n and m are the same as or different from each other and are an integer from 1 to 12, preferably from 2 to 6;

[0045] -R represents a hydrogen atom; or is selected from C 1 -C 20 , preferably C 1 -C 10 A linear or branched, saturated or unsaturated alkyl group optionally containing heteroatoms, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclyl group; preferably hydrogen;

[0046] -R 1 , which are the same or different from each other, represent a hydrogen atom; or are selected from C 1 -C 20 , preferably C 1 -C 10 A straight or branched, saturated or unsaturated alkyl group optionally containing heteroatoms, preferably hydrogen or methyl;

[0047] -R 2 represents a hydrogen atom; or is selected from C 1 -C 20 , preferably C 1 -C 10 The straight chain or branched, saturated or unsaturated alkyl group which may contain heteroatoms is preferably methyl.

[0048] For the purposes of the present description and the following claims, definitions of numerical ranges always include the extreme values, unless otherwise indicated.

[0049] For the purposes of this specification and the following claims, the term "comprising" also encompasses the terms "which consists essentially of" or "which consists of.

[0050] For the purposes of this specification and the following claims, the term “C 1 -C 20 "Alkyl" refers to a straight chain or branched, saturated or unsaturated alkyl group having 1 to 20 carbon atoms. 1 -C 20 Specific examples of the alkyl group are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, ethylhexyl, hexyl, heptyl, n-octyl, nonyl, decyl, dodecyl, 2-octyldodecyl, 2-ethyldodecyl, 2-butyloctyl, 2-hexyldecyl.

[0051] For the purposes of this specification and the following claims, the term "C optionally containing heteroatoms" 1 -C 20 "Alkyl" refers to a straight or branched, saturated or unsaturated alkyl group having 1 to 20 carbon atoms, wherein at least one hydrogen atom is substituted by a heteroatom selected from the following: halogen, for example, fluorine, chlorine, bromine, preferably fluorine; nitrogen; sulfur; oxygen. The C optionally containing heteroatoms1 -C 20 Specific examples of the alkyl group are fluoromethyl, difluoromethyl, trifluoromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, perfluoropentyl, perfluorooctyl, perfluorodecyl, ethyl-2-methoxy, propyl-3-ethoxy, butyl-2-thiomethoxy, hexyl-4-amino, hexyl-3-N,N'-dimethylamino, methyl-N,N'-dioctylamino, 2-methyl-hexyl-4-amino.

[0052] For the purpose of this specification and the following claims, the term "aryl" refers to an aromatic carbocyclic group containing 6 to 60 carbon atoms. The aryl group may be optionally substituted by one or more groups selected from the following groups, which may be the same or different from each other: halogen atoms, for example, fluorine, chlorine, bromine, preferably fluorine; hydroxyl; C 1 -C 12 Alkyl; C 1 -C 12 Alkoxy; C 1 -C 12 Thioalkoxy; C 3 -C 24 trialkylsilyl; polyethyleneoxy; cyano; amino; C 1 -C 12 a mono- or di-alkylamino group; a nitro group. Specific examples of the aryl group are: phenyl, methylphenyl, mesityl, methoxyphenyl, hydroxyphenyl, phenoxyphenyl, fluorophenyl, pentafluorophenyl, chlorophenyl, bromophenyl, nitrophenyl, dimethylaminophenyl, naphthyl, phenylnaphthyl, phenanthrene, anthracene.

[0053] For the purpose of this specification and the following claims, the term "heteroaryl" refers to a heterocyclic aromatic five- or six-atom group, which may also be a benzo-fused ring or a heterobicyclic ring, containing 4 to 60 carbon atoms and 1 to 4 heteroatoms selected from nitrogen, oxygen, sulfur, silicon, selenium, phosphorus. The heteroaryl group may be optionally substituted by one or more groups selected from the following, which may be the same or different from each other: halogen atoms, for example, fluorine, chlorine, bromine, preferably fluorine; hydroxyl; C 1 -C 12 Alkyl; C 1 -C 12 Alkoxy; C 1 -C 12 Thioalkoxy; C 3 -C 24 trialkylsilyl; polyethyleneoxy; cyano; amino; C 1 -C 12a mono- or di-alkylamino group; a nitro group. Specific examples of heteroaryl groups are: pyridine, picoline, methoxypyridine, phenylpyridine, fluoropyridine, pyrimidine, pyridazine, pyrazine, triazine, tetrazine, quinoline, quinoxaline, quinazoline, furan, thiophene, hexylthiophene, bromothiophene, dibromothiophene, pyrrole, oxazole, thiazole, isothiazole, oxadiazole, thiadiazole, pyrazole, imidazole, triazole, tetrazole, indole, benzofuran, benzothiophene, benzoxazole, benzothiazole, benzooxadiazole, benzothiadiazole, benzopyrazole, benzimidazole, benzotriazole, triazolopyrimidine, and coumarin.

[0054] For the purposes of this specification and the following claims, the term "cycloalkyl" refers to a cycloalkyl group having 3 to 30 carbon atoms. The cycloalkyl group may be optionally substituted by one or more groups selected from the following groups, which may be identical or different from each other: a halogen atom, for example, fluorine, chlorine, bromine, preferably fluorine; a hydroxyl group; a C 1 -C 12 Alkyl; C 1 -C 12 Alkoxy; C 1 -C 12 Thioalkoxy; C 3 -C 24 trialkylsilyl; polyethyleneoxy; cyano; amino; C 1 -C 12 a mono- or di-alkylamino group; a nitro group. Specific examples of the cycloalkyl group are: a cyclopropyl group, a 2,2-difluorocyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a methoxycyclohexyl group, a fluorocyclohexyl group, a phenylcyclohexyl group, a decalinyl group, a rosinyl group.

[0055] For the purpose of this specification and the above claims, the term "heterocyclic group" refers to a saturated or unsaturated ring having 3 to 12 atoms, which contains at least one heteroatom selected from nitrogen, oxygen, sulfur, silicon, selenium, phosphorus, optionally fused to other aromatic or non-aromatic rings. The heterocyclic group may be optionally substituted by one or more groups selected from the following, which may be identical or different from each other: halogen atoms (e.g. fluorine, chlorine, bromine, preferably fluorine), hydroxyl, C 1 -C 12 Alkyl; C 1 -C 12 Alkoxy; C 1 -C 12 Thioalkoxy; C 3 -C 24 Polyethyleneoxy; cyano; amino; C 1 -C 12Specific examples of heterocyclic groups are: pyrrolidine, methoxypyrrolidine, piperidine, fluoropiperidine, methylpiperidine, dihydropyridine, piperazine, morpholine, thiazine, indoline, phenylindoline, 2-ketoazetidine, diketopiperazine, tetrahydrofuran, tetrahydrothiophene.

[0056] For the purposes of this specification and the following claims, the term “C 1 -C 20 "Dialkyl-amino" refers to an amino group containing two C 1 -C 12 A group of nitrogen atoms to which an alkyl group is bonded. Specific examples of the dialkylamino group are: dimethylamino, diethylamino, dibutylamino, diisobutylamino.

[0057] For the purposes of this specification and the following claims, the term “C 1 -C 20 "Alkoxy" refers to a group containing an oxygen atom, a straight or branched, saturated or unsaturated C 1 -C 20 An alkyl group is bonded to the oxygen atom. 1 -C 20 Specific examples of the alkoxy group are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy.

[0058] According to a preferred embodiment of the present invention, the fullerene content of the fullerene functionalized (meth)acrylic polymer having the general formula (I) is greater than or equal to 35 wt %, preferably 40 wt % to 70 wt %, relative to the total weight of the fullerene functionalized (meth)acrylic polymer having the general formula (I).

[0059] According to a preferred embodiment of the present invention, the hydroxyl (-OH) content of the fullerene functionalized (meth)acrylic polymer having the general formula (I) is greater than or equal to 0.01 wt %, preferably 0.05 wt % to 12 wt %, relative to the total weight of the fullerene functionalized (meth)acrylic polymer having the general formula (I).

[0060] As mentioned above, the present invention also relates to a method for preparing the fullerene-functionalized (meth)acrylic polymer having the general formula (I).

[0061] Therefore, another object of the present invention is a process for preparing a fullerene-functionalized (meth)acrylic polymer of the general formula (I), which comprises subjecting at least one (meth)acrylic polymer of the general formula (II):

[0062]

[0063] in:

[0064] - x is a fraction from 0 to 0.9, preferably from 0 to 0.6;

[0065] -y is an integer or fraction from 0.1 to 1, preferably from 0.15 to 1;

[0066] -The premise is that the sum of x+y is equal to 1;

[0067] - p is an integer from 10 to 5000, preferably from 20 to 2500;

[0068] -n, R 1 and R 2 has the same meaning as above;

[0069] and at least one fullerene derivative having the general formula (III):

[0070]

[0071] wherein m, R and w have the same meanings as above, and X represents a hydroxide anion or a halogen anion, such as a chloride ion, a bromide ion, an iodide ion, preferably a hydroxide anion or a chloride ion, more preferably a hydroxide anion;

[0072] React in the presence of:

[0073] - organic solvents or mixtures of organic solvents;

[0074] - at least one substituted pyridine having the general formula (IV):

[0075]

[0076] Where R 3 represents a hydrogen atom; or is selected from C 1 -C 20 , preferably C 1 -C 10 a linear or branched, saturated or unsaturated alkyl group optionally containing a heteroatom, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, C 1 -C 20 , preferably C 2 -C 10 A straight-chain or branched, saturated or unsaturated dialkyl-amino group, C 1 -C 20 , preferably C 2 -C 10 A straight or branched, saturated or unsaturated alkoxy group; or represents an amino group, a cyano group, or a hydroxyl group; preferably R 3is methyl, tert-butyl, vinyl, dimethylamino, methoxy, more preferably dimethylamino;

[0077] - at least one substituted carbodiimide of the general formula (V):

[0078]

[0079] Where R 4 and R 5 Same or different from each other, selected from C 1 -C 20 , preferably C 1 -C 10 A linear or branched, saturated or unsaturated alkyl group optionally containing heteroatoms, an optionally substituted aryl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group; preferably, R 4 and R 5 It is ethyl, isopropyl, cyclohexyl, or 3-dimethylaminopropyl, and more preferably cyclohexyl.

[0080] According to a preferred embodiment of the present invention, the organic solvent may be selected from, for example, dimethyl sulfoxide (DMSO), xylene, toluene, mesitylene, tetrahydrofuran (THF), methyltetrahydrofuran (Me-THF), and dioxane.

[0081] According to a particularly preferred embodiment of the present invention, the organic solvent mixture is a mixture of organic solvents which can be selected from, for example, the following: dimethyl sulfoxide (DMSO), xylene, toluene, mesitylene, in a ratio of 1 / 1 v / v, more preferably a mixture of dimethyl sulfoxide (DMSO) / toluene (1 / 1 v / v), a mixture of dimethyl sulfoxide (DMSO) / xylene (1 / 1 v / v).

[0082] According to a preferred embodiment of the present invention, the (meth)acrylic polymer having the general formula (II) and the fullerene derivative having the general formula (III) may be used in a molar ratio of 10 to 0.1, preferably 5 to 0.25, and even more preferably 2.5 to 0.8 relative to the molar amount of -OH groups contained in the (meth)acrylic polymer having the general formula (II).

[0083] According to a preferred embodiment of the present invention, the substituted pyridine having the general formula (IV) can be selected from, for example, 4-dimethylaminopyridine (DMAP), 4-methylpyridine, 4-tert-butylpyridine, 4-vinylpyridine, 4-methoxypyridine, 4-hydroxypyridine or a mixture thereof; preferably it is 4-dimethylaminopyridine (DMAP).

[0084] According to a preferred embodiment of the present invention, the carbodiimide having the general formula (V) can be selected from, for example, N,N'-diethylcarbodiimide, N,N'-diisopropylcarbodiimide, N,N'-diisopropylcarbodiimide, N,N'-di-3-dimethylaminopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide (DCC) or a mixture thereof; preferably N,N'-dicyclohexylcarbodiimide (DCC).

[0085] According to a preferred embodiment of the present invention, the substituted pyridine having the general formula (IV) may be used in a molar ratio of 0.9 to 0.1, preferably 0.6 to 0.4, relative to the total moles of the fullerene derivative having the general formula (III).

[0086] According to a preferred embodiment of the present invention, the carbodiimide having the general formula (V) may be used in a molar ratio of 9 to 1, preferably 6 to 4, relative to the total moles of the fullerene derivative having the general formula (III).

[0087] According to a preferred embodiment of the present invention, the method may be carried out at a temperature of 15°C to 150°C, preferably 20°C to 90°C.

[0088] According to a preferred embodiment of the present invention, the method may be carried out for a period of 2 hours to 96 hours, preferably 20 hours to 90 hours.

[0089] As described above, the fullerene-functionalized (meth) acrylic polymer having the general formula (I) can be advantageously used as an electron acceptor compound in an organic photovoltaic device (or solar device) on a rigid support or a flexible support (e.g., a binary, ternary, quaternary organic photovoltaic cell (or solar cell), an organic photovoltaic module (or solar module) having a simple or "tandem" structure). In addition, the fullerene-functionalized (meth) acrylic polymer having the general formula (I) can be advantageously used in a perovskite-based photovoltaic cell (or solar cell) in an electron transport layer (ETL). In addition, the fullerene-functionalized (meth) acrylic polymer having the general formula (I) can be advantageously used in the production of an organic thin film transistor (OTFT) or an organic field effect transistor (OFET).

[0090] Therefore, another object of the present invention is an organic photovoltaic device (or solar device) on a rigid support or a flexible support (for example, an organic binary, ternary, quaternary solar cell, an organic photovoltaic module (or solar module) with a simple or "tandem" structure), which comprises at least one fullerene-functionalized (meth) acrylic polymer having the specific general formula (I).

[0091] Another object of the present invention is a perovskite-based photovoltaic cell (or solar cell) in which the electron transport layer (ETL) comprises at least one fullerene-functionalized (meth)acrylic polymer having the specific general formula (I).

[0092] Another object of the present invention is an organic thin film transistor (OTFT) or an organic field effect transistor (OFET) comprising at least one fullerene-functionalized (meth)acrylic polymer of the specific general formula (I).

[0093] In order to better understand the invention and put it into practice, some illustrative and non-limiting examples are reported below.

[0094] The following characterization methods were used in the following examples.

[0095] NMR spectroscopy

[0096] NMR spectra of the obtained compounds were carried out using a Bruker Avance 400 NMR spectrometer.

[0097] For this purpose, about 10 mg of the sample to be measured are dissolved directly in about 0.8 ml of a suitable deuterated solvent on the glass tube used for the measurement. The chemical shift scale is calibrated relative to the tetramethylsilane signal which is set to 0 ppm.

[0098] FT-IR spectroscopy

[0099] FT-IR spectra were recorded using Thermo Nicolet Nexus 670 and Bruker IFS 48 spectrophotometers.

[0100] FT-IR spectra of the polymers were obtained from polymer films on potassium bromide (KBr) sheets obtained by depositing solutions of the polymer to be analyzed in hot 1,2-dichlorobenzene. The concentration of the polymer solutions analyzed was 10 wt % relative to the total weight of the polymer solution.

[0101] Thermogravimetric analysis (TGA)

[0102] Thermogravimetric analysis (TGA) using TA The Q500 instrument was operated by gradually increasing the temperature from 50°C to 300°C (at a rate of 20°C / min) under a nitrogen atmosphere and continuously recording the weight change of the sample.

[0103] Example 1

[0104] Preparation of copolymer P(MMA / HEMA)(CC334)

[0105]

[0106] The synthesis of copolymer P(MMA / HEMA) (CC334) was carried out by free radical polymerization of monomers methyl methacrylate (MMA) (TCI Europe, purity>99.8%) and 2-hydroxyethyl methacrylate (HEMA) (TCI Europe, purity>95%). The synthesis was carried out after purification of the monomers MMA and HEMA by filtration on neutral alumina (Merck) and using α,α'-azobisisobutyronitrile (AIBN) (Sigma Aldrich, purity>98%) recrystallized from methanol (MeOH) (VWR, purity>99.8%) as free radical initiator.

[0107] To this end, MMA (50 mmol), HEMA (50 mmol) and a free radical initiator (AIBN) (0.3 mol%) were dissolved in 10.5 ml of 1,4-dioxane (Merck, purity>99%) in a 250 ml two-necked flask equipped with a magnetic stirrer under an inert atmosphere: the reaction mixture was kept at 75° C. for 16 hours under stirring. Subsequently, the temperature was allowed to drop naturally to room temperature (25° C.) and 50 ml of tetrahydrofuran (THF) [Merck, purity 99.9%, containing 250 ppm of butylated hydroxytoluene (BHT)] were added to the resulting reaction crude (colorless gel) until a homogeneous solution was obtained. Cold n-hexane (VWR, purity>95%) (100 ml) was added to the homogeneous solution obtained, resulting in the precipitation of a white solid. The white solid was filtered, washed with cold n-hexane (VWR, 95% purity) (3×20 ml), and dried in an oven at 60° C. overnight to obtain 11.3 g of copolymer P(MMA / HEMA)(CC334)(1:1MMA / HEMA), corresponding to a yield of 98%.

[0108] Copolymer P(MMA / HEMA)(CC334) 1 H-NMR spectra [400 MHz, at d 4 Methanol (VWR, purity 99.8%)] was characterized and obtained Figure 1 The spectrum shown thus confirms that the two monomers are present in a molar ratio of 1:1: it can be deduced that, with respect to the (meth)acrylic polymer having the general formula (II), x=y=0.5.

[0109] The copolymer P(MMA / HEMA)(CC334) was also characterized by thermogravimetric analysis ( Figure 2 ) and FT-IR spectra ( Figure 3 ) characterization.

[0110] Example 2

[0111] Preparation of homopolymer PHEMA (CC344)

[0112]

[0113] The synthesis of homopolymer PHEMA (CC344) was carried out by free radical polymerization of the monomer 2-hydroxyethyl methacrylate (HEMA) (TCI Europe, purity>95%). The synthesis was carried out after purification of the HEMA monomer by filtration on neutral alumina (Merck) and using α,α'-azobisisobutyronitrile (AIBN) (Sigma Aldrich, purity>98%) recrystallized from methanol (MeOH) (VWR, purity>99.8%) as a free radical initiator.

[0114] For this purpose, HEMA (43 mmol) and a free radical initiator (AIBN) (0.3 mol%) were dissolved in 15 ml of anhydrous ethanol (Merck) in a 250 ml two-necked flask equipped with a magnetic stirrer under an inert atmosphere: the reaction mixture was kept at 60° C. for 16 hours under stirring. Subsequently, the temperature was allowed to drop naturally to room temperature (25° C.) and cold n-hexane (VWR, purity>95%) (100 ml) was added to the resulting reaction mixture, resulting in a white solid precipitate. The white solid was filtered, washed with cold n-hexane (VWR, purity 95%) (3×20 ml) and dried in an oven at 60° C. overnight to give the homopolymer PHEMA (CC344), corresponding to a yield of 95%. With respect to the (meth)acrylic polymer having the general formula (II), x=0 and y=1 were inferred.

[0115] Homopolymer PHEMA (CC344) 1 H-NMR spectra [400 MHz, at d 4 Methanol (VWR, purity 99.8%)] was characterized and obtained Figure 4 Spectrum shown.

[0116] The homopolymer PHEMA (CC344) was also characterized by thermogravimetric analysis ( Figure 5 ).

[0117] Example 3

[0118] Preparation of Fullerene Derivative PCBA

[0119]

[0120] The fullerene derivative PCBA was prepared according to the method reported by Hummelen JC et al., "The Journal of Organic Chemistry" (1995), Vol. 60, pp. 532-538, by hydrolyzing [6,6]-phenyl-C 61-Butyric acid methyl ester (PC61BM) was used for the experiment.

[0121] To this end, 56 ml of concentrated hydrochloric acid (HCl) (VWR, 37% in water) and 139 ml of glacial acetic acid (Merck, purity >97%) were added to a 1-liter two-necked flask equipped with a magnetic stirrer. 61 -Butyric acid methyl ester (PC61BM) (2 g, 2.2 mmol) (Solenne Bv, purity> 99%) in 330 ml of toluene (VWR, purity> 99.5%): the reaction mixture obtained was heated and kept at reflux for 48 hours under stirring. Subsequently, the temperature was naturally reduced to room temperature (25°C) and the solvent was removed by vacuum evaporation: the residue was washed with diethyl ether (Merck, purity> 99%) (3×10 ml), toluene (Merck, purity> 99%) (3×10 ml), and again with diethyl ether (Merck, purity> 99%) (2×10 ml), and finally dried under vacuum at room temperature (25°C) for 6 hours to obtain 1.85 g of the fullerene derivative PCBA, corresponding to a yield of 94%.

[0122] Fullerene derivative PCBA was analyzed by thermogravimetric analysis ( Figure 2 ) and FT-IR spectra ( Figure 3 ) for characterization.

[0123] Example 4

[0124] Fullerene functionalized methacrylic acid polymer C 60 Preparation of -P(MMA-HEMA)(CC361)

[0125]

[0126] The introduction of fullerene units into the copolymer P(MMA / HEMA)(CC334) was carried out as follows to prepare the fullerene functionalized methacrylic acid polymer C 60 -P(MMA-HEMA)(CC361).

[0127] To this end, PCBA (275 mg, 0.304 mmol) obtained as described in Example 3, P(MMA / HEMA) (100 mg, 0.434 mmol of -OH groups) obtained as described in Example 1 and 4-dimethylaminopyridine (DMAP) (Merck, purity>99%) (0.16 mmol) were dissolved in an inert atmosphere in 25 ml of a mixture of dimethyl sulfoxide (DMSO) (Merck, purity>99%) / toluene (VWR, purity>99.5%) (1:1, v / v) in a 100 ml two-necked flask equipped with a magnetic stirrer. Subsequently, a solution of N,N'-dicyclohexylcarbodiimide (DCC) (Merck, purity 99%) (1.63 mmol) in a mixture of 10 ml of dimethyl sulfoxide (DMSO) (Merck, purity>99%) / toluene (VWR, purity>99.5%) (1:1, v / v) was added dropwise to the reaction mixture. Under stirring, the obtained reaction mixture was kept at 40° C. in an inert atmosphere for 72 hours. Subsequently, the temperature was allowed to naturally drop to room temperature (25° C.), 50 ml of distilled water was added to the reaction mixture, the two phases were separated with a separatory funnel, the aqueous phase was treated with toluene (VWR, purity>99.5%) (3×10 ml), and the obtained organic phase was combined with the reaction mixture. Subsequently, toluene was removed by vacuum evaporation at room temperature (25° C.). The obtained solid residue was treated with 25 ml of tetrahydrofuran (THF) [Merck, purity 99.9%-, containing 250 ppm butylhydroxytoluene (BHT), previously filtered on neutral alumina to remove BHT present in commercial products] to remove any unreacted PCBA, and the obtained suspension was kept at room temperature (25° C.) for 1 hour under stirring. Subsequently, the suspension was centrifuged and the trace insoluble matter deposited at the bottom of the container was removed by standing. The resulting clear solution was concentrated to a volume of 5 ml under vacuum at room temperature (25° C.) and added dropwise to cold n-hexane (Merck, purity 95%) (100 ml) to obtain a brown solid precipitate. The brown solid was recovered by vacuum filtration on a Buchner filter and washed on the filter with cold n-hexane (VWR, purity 95%) (2×20 ml), methanol (Merck) (2×15 ml) and diethyl ether (Merck, >99%) (2×10 ml), and finally dried in an oven at 60° C. overnight to obtain 251 mg of fullerene-functionalized methacrylic acid polymer C. 60 -P(MMA-HEMA)(CC361), corresponding to a yield of 68%.

[0128] Fullerene functionalized methacrylic acid polymer C 60 -P(MMA-HEMA)(CC361) passed 1 H-NMR-spectroscopy [400 MHz, at d1 Chloroform (VWR, purity> 99.8%)] characterization, obtain Figure 6 Spectrum shown.

[0129] The fullerene-functionalized methacrylic acid polymer C60-P(MMA-HEMA)(CC361) was also characterized by thermogravimetric analysis ( Figure 2 ), from which it can be determined that the residual fullerene content in the polymer is equal to 60% by weight: From this data, it is deduced that, with respect to the fullerene-functionalized methacrylic polymer of formula (I), x=0.5, y=0.15 and z=0.35, while, from this data, the content of -OH groups is calculated, and it is found that relative to the fullerene-functionalized (meth)acrylic polymer C 60 -P(MMA-HEMA)(CC361), the content of -OH groups is equal to 0.6% by weight.

[0130] Fullerene functionalized methacrylic acid polymer C 60 -P(MMA-HEMA)(CC361) was also characterized by IR spectroscopy ( Figure 3 ), where the presence of fullerene units in the polymer can be seen by the 525 cm -1 The presence of the absorption band was qualitatively confirmed.

[0131] Example 5

[0132] Fullerene functionalized methacrylic acid polymer C 60 Preparation of -P(MMA-HEMA)(CC461)

[0133]

[0134] The introduction of fullerene units into the copolymer P(MMA / HEMA)(CC334) was carried out as follows to prepare the fullerene functionalized methacrylic acid polymer C 60 -P(MMA-HEMA)(CC461).

[0135] For this purpose, PCBA (253 mg, 0.282 mmol) obtained as described in Example 3, P(MMA / HEMA) (100 mg, 0.434 mmol of OH groups) obtained as described in Example 1 and 4-dimethylaminopyridine (DMAP) (Merck, purity>99%) (0.16 mmol) were dissolved in an inert atmosphere in a mixture of 25 ml of dimethyl sulfoxide (DMSO) (Merck, purity>99%) / xylene (Merck, purity>98%) (1:1, v / v) in a 100 ml two-necked flask equipped with a magnetic stirrer. Subsequently, a solution of N,N'-dicyclohexylcarbodiimide (DCC) (Merck, 99% purity) (1.63 mmol) in a mixture of 10 ml of dimethyl sulfoxide (DMSO) (Merck,>99% purity) / xylene (Merck,>98% purity) (1:1, v / v) was added dropwise to the reaction mixture. The resulting reaction mixture was kept at 40° C. in an inert atmosphere for 72 hours under stirring. Subsequently, the operation was carried out as described in Example 4 to obtain 225 mg of fullerene-functionalized methacrylic acid polymer C 60 -P(MMA-HEMA)(C461), corresponding to a yield of 64%.

[0136] Fullerene functionalized methacrylic acid polymer C 60 -P(MMA-HEMA)(CC461) was characterized by thermogravimetric analysis ( Figure 2 ), from which it can be determined that the residual fullerene content in the polymer is equal to 58% by weight: From this data, it is deduced that, with respect to the fullerene-functionalized (meth)acrylic polymer having the general formula (I), x=0.5, y=0.18 and z=0.32. At the same time, the content of -OH groups is calculated from this data and it is found that relative to the fullerene-functionalized methacrylic polymer C 60 -P(MMA-HEMA)(CC461), the content of -OH groups is equal to 0.8% by weight.

[0137] Example 6

[0138] Fullerene functionalized methacrylic acid polymer C 60 Preparation of -P(MMA-HEMA)(CC371)

[0139]

[0140] The introduction of fullerene units into the copolymer P(MMA / HEMA)(CC334) was carried out as follows to prepare the fullerene functionalized methacrylic acid polymer C 60 -P(MMA-HEMA)(CC371).

[0141] To this end, PCBA obtained as described in Example 3 (214 mg, 0.239 mmol), P(MMA / HEMA) obtained as described in Example 1 (50 mg, 0.217 mmol of OH groups) and 4-dimethylaminopyridine (DMAP) (Merck, purity>99%) (0.14 mmol) were dissolved in an inert atmosphere in 20 ml of a mixture of dimethyl sulfoxide (DMSO) (Merck-purity>99%) / xylene (Merck, purity>98%) (1:1, v / v) in a 100 ml two-necked flask equipped with a magnetic stirrer. Subsequently, a mixture solution of N,N'-dicyclohexylcarbodiimide (DCC) (Merck, 99% purity) (1.38 mmol) in 20 ml of dimethyl sulfoxide (DMSO) (Merck, >99% purity) / xylene (Merck, >98% purity) (1:1, v / v) was added dropwise to the reaction mixture, and the resulting reaction mixture was kept stirred at 40°C in an inert atmosphere for 72 hours. Subsequently, the operation was carried out as described in Example 4 to obtain 180 mg of copolymer C 60 -P(MMA / HEMA)(CC371), corresponding to a yield of 72%.

[0142] Fullerene functionalized methacrylic acid polymer C 60 -P(MMA-HEMA)(CC371) passed 1 H-NMR-spectroscopy [400 MHz, at d 1 Chloroform (VWR, purity> 99.8%)] characterization, obtain Figure 7 Spectra reported in .

[0143] Fullerene functionalized methacrylic acid polymer C 60 -P(MMA-HEMA)(CC371) was also characterized by thermogravimetric analysis ( Figure 2 ), from which the amount of residual fullerene in the polymer was determined to be equal to 64% by weight: From this data, it is deduced that, with respect to the fullerene-functionalized (meth)acrylic polymer of formula (I), x=0.5, y=0.02 and z=0.48, while from this data the content of -OH groups is calculated, and it is found that relative to the fullerene-functionalized methacrylic polymer C 60 -P(MMA-HEMA)(CC371), the content of -OH groups is equal to 0.06% by weight.

[0144] Example 7

[0145] Fullerene functionalized methacrylic acid polymer C 60 Preparation of -P(HEMA)(CC363)

[0146]

[0147] The introduction of fullerene units into the polymer PHEMA (CC344) was carried out as follows to prepare the fullerene functionalized methacrylate polymer C 60 -PHEMA (CC363).

[0148] To this end, PHEMA (100 mg, 0.768 mmol of -OH groups) obtained as described in Example 2 was dissolved in an inert atmosphere in 15 ml of a mixture of dimethyl sulfoxide (DMSO) (Merck, purity >99%) / toluene (VWR, purity >99.5%) (1:1, v / v) in a 100 ml two-necked flask equipped with a magnetic stirrer, and the mixture was kept at 40° C. for 14 h under stirring. Subsequently, PCBA (517 mg, 0.576 mmol) and 4-dimethylaminopyridine (DMAP) (Merck, purity> 99%) (0.24 mmol) obtained as described in Example 3 were added, and a mixture solution of N,N'-dicyclohexylcarbodiimide (DCC) (Merck, purity 99%) (2.41 mmol) in 10 ml of dimethyl sulfoxide (DMSO) (Merck, purity> 99%) / toluene (VWR, purity> 99.5%) (1:1) was added dropwise: the reaction mixture obtained was kept stirring at 40° C. in an inert atmosphere for 72 hours. Subsequently, the operation was carried out as described in Example 4 to obtain 394 mg of copolymer C 60 -PHEMA(CC363), corresponding to a yield of 65%.

[0149] Fullerene functionalized methacrylic acid polymer C 60 -PHEMA (CC363) passed 1 H-NMR spectra [400 MHz, at d 1 Chloroform (VWR, purity> 99.8%)] characterization, obtain Figure 8 Spectra reported in .

[0150] Fullerene functionalized methacrylic acid polymer C 60 -PHEMA(CC363) was also characterized by thermogravimetric analysis ( Figure 5 ), from which it can be inferred that the amount of residual fullerene in the polymer is 69 wt %: From this data, it can be inferred that for the fullerene functionalized (meth) acrylic polymer having the general formula (I), x=0, y=0.25 and z=0.75, and the content of -OH groups is calculated from this data and found to be 69 wt % relative to the fullerene functionalized (meth) acrylic polymer C 60 -P(MMA-HEMA)(CC363), the content of -OH groups is equal to 0.5 wt%.

[0151] Example 8

[0152] Fullerene functionalized methacrylic acid polymer C 60 Preparation of -PHEMA (CC566)

[0153]

[0154] The introduction of fullerene units into the copolymer PHEMA (CC344) was carried out as follows to prepare the fullerene functionalized methacrylic acid polymer C 60 -PHEMA (CC566).

[0155] To this end, PHEMA (100 mg, 0.768 mmol of -OH groups) obtained as described in Example 2 was dissolved in an inert atmosphere in 15 ml of a mixture of dimethyl sulfoxide (DMSO) (Merck, purity >99%) / xylene (Merck, purity >98%) (1:1, v / v) in a 100 ml two-necked flask equipped with a magnetic stirrer, and the mixture was kept at 40° C. for 14 h under stirring. Subsequently, PCBA (633 mg, 0.706 mmol) and 4-dimethylaminopyridine (DMAP) (Merck, purity>99%) (0.24 mmol) obtained as described in Example 3 were added, and a solution of N,N'-dicyclohexylcarbodiimide (DCC) (Merck, purity 99%) (2.41 mmol) in a mixture of 10 ml of dimethyl sulfoxide (DMSO) (Merck, purity>99%) / xylene (Merck, purity>98%) (1:1, v / v) was added dropwise: the reaction mixture obtained was kept stirring at 40° C. in an inert atmosphere for 72 hours. Subsequently, the operation was carried out as described in Example 4 to obtain 540 mg of fullerene-functionalized methacrylic acid polymer C 60 -PHEMA(CC566), corresponding to a yield of 75%.

[0156] Fullerene functionalized methacrylic acid polymer C 60 -PHEMA (CC566) passed 1 H-NMR spectra [400 MHz, at d 1 Chloroform (VWR, purity> 99.8%)] characterization, obtain Fig. 9 Spectra reported in .

[0157] Fullerene functionalized methacrylic acid polymer C 60 -PHEMA(CC566) was also characterized by thermogravimetric analysis ( Figure 5), from which it can be determined that the amount of residual fullerene in the polymer is equal to 71% by weight: From this data, it is deduced that, with respect to the fullerene-functionalized (meth)acrylic polymer having the general formula (I), x=0, y=0.08 and z=0.92, and from this data the content of -OH groups is calculated, and it is found that relative to the fullerene-functionalized methacrylic polymer C 60 -P(MMA-HEMA)(CC566), the content of -OH groups is equal to 0.14% by weight.

Claims

1. Fullerene functionalized (meth)acrylic polymer having the general formula (I): in: - x is a fraction from 0 to 0.89, preferably from 0 to 0.6; -y is a fraction from 0.01 to 0.9, preferably from 0.015 to 0.5; - z is a fraction from 0.1 to 0.99, preferably from 0.25 to 0.95; -The premise is that the sum of x+y+z is equal to 1; - p is an integer from 10 to 5000, preferably from 20 to 2500; -w is an integer from 50 to 250, preferably from 60 to 90, more preferably 60, 70, 84; - n and m are the same as or different from each other and are an integer from 1 to 12, preferably from 2 to 6; -R represents a hydrogen atom; or is selected from C 1 -C 20 , preferably C 1 -C 10 A linear or branched, saturated or unsaturated alkyl group optionally containing heteroatoms, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclyl group; preferably hydrogen; -R 1 , which are the same or different from each other, represent a hydrogen atom; or are selected from C 1 -C 20 , preferably C 1 -C 10 A straight or branched, saturated or unsaturated alkyl group optionally containing heteroatoms, preferably hydrogen or methyl; -R 2 represents a hydrogen atom; or is selected from C 1 -C 20 , preferably C 1 -C 10 The straight chain or branched, saturated or unsaturated alkyl group which may contain heteroatoms is preferably methyl.

2. The fullerene-functionalized (meth)acrylic polymer of claim 1 , wherein the fullerene content of the fullerene-functionalized (meth)acrylic polymer of the general formula (I) is greater than or equal to 35% by weight, preferably 40% to 70% by weight, relative to the total weight of the fullerene-functionalized (meth)acrylic polymer of the general formula (I).

3. The fullerene-functionalized (meth)acrylic polymer of claim 1 or 2, wherein the hydroxyl (-OH) content of the fullerene-functionalized (meth)acrylic polymer of the general formula (I) is greater than or equal to 0.01 wt %, preferably 0.05 wt % to 12 wt %, relative to the total weight of the fullerene-functionalized (meth)acrylic polymer of the general formula (I).

4. A method for preparing a fullerene-functionalized (meth)acrylic polymer of formula (I) according to any one of the preceding claims, comprising subjecting at least one (meth)acrylic polymer of formula (II): in: - x is a fraction from 0 to 0.9, preferably from 0 to 0.6; -y is an integer or fraction from 0.1 to 1, preferably from 0.15 to 1; -The premise is that the sum of x+y is equal to 1; - p is an integer from 10 to 5000, preferably from 20 to 2500; -n, R 1 and R 2 has the same meaning as above; and at least one fullerene derivative having the general formula (III): wherein m, R and w have the same meanings as above, and X represents a hydroxide anion or a halogen anion, such as a chloride ion, a bromide ion, an iodide ion, preferably a hydroxide anion or a chloride ion, more preferably a hydroxide anion; React in the presence of: - organic solvents or mixtures of organic solvents; - at least one substituted pyridine having the general formula (IV): Where R 3 represents a hydrogen atom; or is selected from C 1 -C 20 , preferably C 1 -C 10 a linear or branched, saturated or unsaturated alkyl group optionally containing a heteroatom, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, C 1 -C 20 , preferably C 2 -C 10 A straight-chain or branched, saturated or unsaturated dialkyl-amino group, C 1 -C 20 , preferably C 2 -C 10 A straight or branched, saturated or unsaturated alkoxy group; or represents an amino group, a cyano group, or a hydroxyl group; preferably R 3 is methyl, tert-butyl, vinyl, dimethylamino, methoxy, more preferably dimethylamino; - at least one substituted carbodiimide of the general formula (V): Where R 4 and R 5 Same or different from each other, selected from C 1 -C 20 , preferably C 1 -C 10 A linear or branched, saturated or unsaturated alkyl group optionally containing heteroatoms, an optionally substituted aryl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group; preferably, R 4 and R 5 It is ethyl, isopropyl, cyclohexyl or 3-dimethylaminopropyl, and more preferably cyclohexyl.

5. The method for preparing a fullerene-functionalized (meth)acrylic polymer having the general formula (I) according to claim 4, wherein the organic solvent is selected from dimethyl sulfoxide (DMSO), xylene, toluene, mesitylene, tetrahydrofuran (THF), methyltetrahydrofuran (Me-THF), and dioxane.

6. The method for preparing a fullerene-functionalized (meth)acrylic polymer having the general formula (I) according to claim 4, wherein the organic solvent mixture is a mixture of organic solvents selected from the group consisting of dimethyl sulfoxide (DMSO), xylene, toluene, mesitylene, in a ratio of 1 / 1 v / v, more preferably a mixture of dimethyl sulfoxide (DMSO) / toluene (1 / 1 v / v), a mixture of dimethyl sulfoxide (DMSO) / xylene (1 / 1 v / v).

7. A method for preparing a fullerene-functionalized (meth)acrylic polymer of formula (I) according to any one of claims 4 to 6, wherein the (meth)acrylic polymer of formula (II) and the fullerene derivative of formula (III) are used in a molar ratio relative to the molar amount of -OH groups contained in the (meth)acrylic polymer of formula (II), the molar ratio being from 10 to 0.1, preferably from 5 to 0.25, and even more preferably from 2.5 to 0.

8.

8. A method for preparing a fullerene-functionalized (meth)acrylic polymer having the general formula (I) according to any one of claims 4 to 7, wherein the substituted pyridine having the general formula (IV) is selected from 4-dimethylaminopyridine (DMAP), 4-methylpyridine, 4-tert-butylpyridine, 4-vinylpyridine, 4-methoxypyridine, 4-hydroxypyridine or a mixture thereof; preferably 4-dimethylaminopyridine (DMAP).

9. A method for preparing a fullerene-functionalized (meth)acrylic polymer having the general formula (I) according to any one of claims 4 to 8, wherein the carbodiimide having the general formula (V) is selected from N,N'-diethylcarbodiimide, N,N'-diisopropylcarbodiimide, N,N'-di-3-dimethylaminopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide (DCC) or a mixture thereof; preferably N,N'-dicyclohexylcarbodiimide (DCC).

10. A method for preparing a fullerene-functionalized (meth)acrylic polymer of formula (I) according to any one of claims 4 to 9, wherein the substituted pyridine of formula (IV) is used in a molar ratio of 0.9 to 0.1, preferably 0.6 to 0.4, relative to the total moles of the fullerene derivative of formula (III).

11. A method for preparing a fullerene-functionalized (meth)acrylic polymer of formula (I) according to any one of claims 4 to 10, wherein the carbodiimide of formula (V) is used in a molar ratio of 9 to 1, preferably 6 to 4, relative to the total moles of the fullerene derivative of formula (III).

12. A method for preparing a fullerene-functionalized (meth)acrylic polymer having the general formula (I) according to any one of claims 4 to 11, wherein the method is carried out as follows: - at a temperature of 15°C to 150°C, preferably 20°C to 90°C; and / or - for a period of 2 to 96 hours, preferably 20 to 90 hours.

13. An organic photovoltaic device (or solar device) on a rigid or flexible support, such as an organic binary, ternary, quaternary solar cell, an organic photovoltaic module (or solar module) having a simple or "tandem" structure, comprising at least one fullerene-functionalized (meth) acrylic polymer of the general formula (I) according to any one of claims 1 to 12.

14. Perovskite-based photovoltaic cell (or solar cell), wherein the electron transport layer (ETL) comprises at least one fullerene-functionalized (meth)acrylic polymer having the general formula (I) according to any one of claims 1 to 12.

15. An organic thin film transistor (OTFT) or an organic field effect transistor (OFET) comprising at least one fullerene-functionalized (meth)acrylic polymer of formula (I) according to any one of claims 1 to 12.

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