Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/10—Organic polymers or oligomers
  • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
  • H10K85/211—Fullerenes, e.g. C60
  • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/14—Esterification
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
  • H10K10/40—Organic transistors
  • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
  • H10K10/462—Insulated gate field-effect transistors [IGFETs]
  • H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
  • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3

Definitions

• a further subject matter of the present invention is a process for the preparation of said fullerene-functionalized (meth)acrylic polymer having general formula (I).
• the electron acceptor compound is selected from Ceo, C70 fullerene derivatives such as, for example, [6,6]-phenyl-C6i-butyric acid methyl ester (PC61BM), (6,6)-phenyl-C7i-butyric acid methyl ester (PC71BM).
• said fullerene derivatives show poor solubility in the solvents normally used for producing photovoltaic cells (or solar cells) and a certain tendency to segregate in the aforesaid photoactive layer.
• the category of (meth)acrylic copolymers containing side-chain fullerene is one of the most studied.
• the most immediate strategy i.e. the synthesis of fullerene-functionalized (meth)acrylic monomers and their subsequent copolymerisation by the radical route does not lead to the desired polymers as reported, for example, by Mehrotra S. et al., in “Chemical Communications” (1997), pg. 463-464; Kirkwood K. et al., in “Journal of Polymer Science Part A: Polymer Chemistry” (1997), Vol. 35, Issue 15, pg. 3323-3325.
• alkyl methacrylates such as, for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, or hydroxyalkyl methacrylates such as, for example, 2-hydroxyethyl methacrylate, 3 -hydroxypropyl methacrylate, or 6-hydroxyhexyl methacrylate.
• azido-polymers has the drawback that non-reacted azido groups can subsequently generate crosslinking processes that lead to materials that are not stable over time and cannot be processed and, therefore, cannot be used for the purposes of the present invention.
• SEC Size exclusion chromatography
• methyl methacrylate and 6-azido-hexyl methacrylate were randomly copolymerised via RAFT polymerisation (“Reversible Addition Fragmentation Chain Transfer Polymerisation”) to obtain a copolymer that was reacted with said monoalkynyl-fullerene functionalized via a copper-mediated “click” reaction, obtaining the aforementioned polymethacrylate.
• RAFT polymerisation Reversible Addition Fragmentation Chain Transfer Polymerisation
• the aforementioned polymethacrylate containing a high quantity of Ceo fullerene shows, both in solution and in silicon wafers, an interchain “self-aggregation” behaviour that strongly depends on the quantity of Ceo fullerene in the chain.
• the processes for preparing fullerene derivatives are often complex multistep processes not suitable for an industrial process. Furthermore, said processes often use halogenated solvents which, as mentioned above, are toxic and, therefore, not advisable for an industrial process.
• said fullerene-functionalized (meth)acrylic polymer having general formula (I) has a good solubility, which ensures that the synthesis process does not lead to cross-linked materials.
• said fullerene-functionalized (meth)acrylic polymer having general formula (I) in addition to the typical solubility in halogenated solvents such as chloroform, chlorobenzene and dichlorobenzene, has a good solubility in tetrahydrofuran (THF), methyltetrahydrofuran (Me-THF), dimethylsulfoxide (DMSO), dioxane (i.e. a solubility equal to 30 mg/ml - 40 mg/ml), i.e.
• aryl groups means aromatic carbocyclic groups containing from 6 to 60 carbon atoms. Said aryl groups can optionally be substituted with one or more groups, identical 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; polyethyleneoxy groups; cyano groups; amino groups; C1-C12 mono- or di-alkylamine groups; nitro groups.
• halogen atoms such as, for example, fluorine, chlorine, bromine, preferably fluorine
• hydroxyl groups such as, for example, fluorine, chlorine, bromine, preferably fluorine
• hydroxyl groups such as, for example, fluorine, chlorine, bromine, preferably fluorine
• hydroxyl groups such as, for example, flu
• heteroaryl groups are: pyridine, methylpyridine, methoxypyridine, phenylpyridine, fluoropyridine, pyrimidine, pyridazine, pyrazine, triazine, tetrazine, quinoline, quinoxaline, quinazoline, furan, thiophene, hexylthiophene, bromothiophene, dibromothiophene, pyrrole, oxazole, thiazole, isothiazole, oxadiazole, tiadiazole, pyrazole, imidazole, triazole, tetrazole, indole, benzofuran, benzothiophene, benzooxazole, benzothiazole, benzooxadiazole, benzothiadiazole, benzopyrazole, benzimidazole, benzotriazole, triazolopyridine, triazolopyrimidine, cous,
• cycloalkyl groups are: cyclopropyl, 2,2-difluorocyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, methoxycyclohexyl, fluorocyclohexyl, phenylcyclohexyl, decalin, abietyl.
• heterocyclic groups means 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 be optionally substituted with one or more groups, identical or different from each other, selected from: halogen atoms, such as fluorine, chlorine, bromine, preferably fluorine, hydroxyl groups, C1-C12 alkyl groups; C1-C12 alkoxy groups; C1-C12 thioalkoxy groups; C3-C24 polyethyleneoxy groups; cyano groups; amino groups; C1-C12 mono- or di- alkylamine groups; nitro groups.
• halogen atoms such as fluorine, chlorine, bromine, preferably fluorine, hydroxyl groups, C1-C12 alkyl groups; C1-C12 alkoxy groups; C1-C12 thioalkoxy groups; C3-C24 polyethyleneoxy groups; cyano groups; amino groups; C1-C12 mono- or di- alkylamine groups; nitro groups.
• C1-C20 dialkyl -amino groups means groups comprising a nitrogen atom to which two C1-C12 alkyl groups are bonded.
• Specific examples of dialkyl-amino groups are: dimethylamine, diethylamine, dibutylamine, di-zso-butylamine.
• said fullerene-functionalized (meth)acrylic polymer having general formula (I) has a content of hydroxyl groups (-OH) greater than or equal to 0.01% by weight, preferably comprised between 0.05% by weight and 12% by weight, with respect to the total weight of said fullerene-functionalized (meth)acrylic polymer having general formula (I).
• FT-IR spectra were recorded using Thermo Nicolet Nexus 670 and Bruker IFS 48 spectrophotometers.
• thermogravimetric analysis was carried out using the TA Instruments® Q500 instrument by gradually increasing the temperature from 50°C to 300°C (at a rate of 20°C/minute), under nitrogen atmosphere, and continuously recording the weight variation of the sample.
• the synthesis of the copolymer P(MMA/HEMA) was carried out by radical polymerisation of the monomers methyl methacrylate (MMA) (TCI Europe - purity > 99.8%) and 2-hydroxyethyl methacrylate (HEMA) (TCI Europe - purity > 95%). Said synthesis was carried out after purification of the monomers MMA and HEMA by filtration on neutral alumina (Merck) and using oc,oc'-azo- isobutyronitrile (AIBN) (Sigma Aldrich - purity > 98%) recrystallised from methanol (MeOH) (VWR - purity > 99.8%) as the radical initiator.
• MMA methyl methacrylate
• HEMA 2-hydroxyethyl methacrylate
• the fullerene-functionalized methacrylic polymer C60-P(MMA-HEMA) (CC361) was also characterised by IR spectroscopy ( Figure 3), wherein the presence of fullerene units in the polymer can be qualitatively confirmed by the presence of the absorption band at 525 cm 1 .

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Nanotechnology (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=84830048

Family Applications (1)

Country Status (4)

• 2022
  • 2022-10-11 IT IT102022000020946A patent/IT202200020946A1/it unknown
• 2023
  • 2023-10-10 EP EP23786774.2A patent/EP4602084A1/de active Pending
  • 2023-10-10 CN CN202380071876.2A patent/CN120035616A/zh active Pending
  • 2023-10-10 WO PCT/IB2023/060155 patent/WO2024079618A1/en not_active Ceased

Also Published As

Similar Documents

Legal Events