RU2574593C2 - Fluorinated structured organic film compositions - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a fluorinated structured organic film (SOF) and a method of producing the said film. The SOF comprises a plurality of segments which include at least the first-type segments and a plurality of linkers which include at the least first-type linkers, which form a covalent organic structure and which represent a covalent bond, a separate atom or a group of covalently bonded atoms. The first-type segments contain fluorine.

EFFECT: obtaining fluorinated structured organic films with the uniform distribution of fluorine therein.

19 cl, 2 tbl, 15 dwg, 9 ex

Description

SUMMARY OF THE INVENTION

The invention provides a fluorinated structured organic film (SOP) comprising a plurality of segments comprising at least segments of the first type and a plurality of linkers comprising at least linkers of the first type forming a covalent organic structure (CBS), with at least segments of the first of the type contain fluorine, as well as a method for manufacturing a fluorinated structured organic film, comprising: (a) preparing a liquid-containing reaction mixture containing a plurality of molecular structures polar blocks including at least segments of the first type and several functional groups, wherein the first-type segments contain fluorine; (b) applying the reaction mixture in the form of a crude film; and (c) converting the raw film to dry SOP.

Brief Description of the Drawings

Other features of the present invention will become apparent from the following description with reference to the accompanying drawings, in which illustrative embodiments are illustrated and in which:

in FIG. 1A-P illustrate examples of building blocks with distinguished symmetrical elements.

Detailed description

The term "SOP" generally means a covalent organic structure (CBS), which at the macroscopic level is a film. The expression "macroscopic level" refers to the SOP observed with the naked eye according to the invention.

The term “fluorinated SOP” means, for example, SOP that contains fluorine atoms covalently bonded to one or more types of SOP segments or linkers. Fluorinated SOPs may additionally contain fluorinated molecules that are not covalently bound to SOPs but randomly distributed in the composition of fluorinated SOPs (i.e., composite fluorinated SOPs). At the same time, SOP, which does not contain fluorine atoms covalently bonded to segments or linkers of SOPs of one or several types, but simply contains fluorinated molecules that are not covalently bonded to one or more segments or linkers of SOPs, is a composite rather than fluorinated SOP.

Calculation and adjustment of the fluorine content in SOP compositions is a simple task and does not require synthesis of polymers for special purposes or mixing / dispersion procedures. In addition, SOP compositions can be SOP compositions in which the fluorine contained in them is uniformly dispersed and structured at the molecular level. The fluorine content in SOP can be controlled by changing the molecular structural block used for the synthesis of SOP, or by changing the amount of fluorine in the used structural block.

Fluorinated SOP can be obtained by introducing into the reaction one or more appropriate molecular structural blocks, at least one of the segments of which contains fluorine atoms.

Fluorinated SOPs are highly developed compositions with a network structure in which the first segment, optionally obtained by a reaction involving a fluorinated structural unit, can be associated with a second segment, which is fluorinated, such as a second segment, obtained by a reaction involving a fluorine-containing molecular building block.

Fluorine contained in fluorinated SOPs can be evenly distributed throughout the SOPs. The uniform distribution of fluorine in SOP can be controlled by the process of forming SOP and, accordingly, the fluorine contained can also be structured at the molecular level.

Such structuring can be carried out by using a mixture of molecular structural blocks having the same general primary structure of molecular structural blocks, but differing in the degree of fluorination (i.e., the number of hydrogen atoms replaced by fluorine) of the structural block.

SOPs can have an uneven distribution of fluorine due to the use of highly fluorinated or perfluorinated molecular structural blocks on top of the formed crude layer, as a result of which a large proportion of highly fluorinated or perfluorinated segments will be contained on the given side of the SOP and thereby ensure an uneven distribution of highly fluorinated or perfluorinated segments along the thickness of the SOP with the ability to create a linear or non-linear concentration gradient in SOP obtained after pr formation of the wet layer in dry SOP. Most highly fluorinated or perfluorinated segments can end in the upper half (which is the opposite of the base) of dry SOP, or most highly fluorinated or perfluorinated segments can end in the lower half (which is adjacent to the base) of dry SOP.

Non-fluorinated molecular building blocks can be used on top of the applied wet layer, resulting in the formation of SOP with the conversion of the raw film to an uneven distribution of non-fluorinated segments in dry SOP. Most non-fluorinated segments can end in the upper half (which is the opposite of the base) of dry SOP, or most non-fluorinated segments can end in the lower half (which is adjacent to the base) of dry SOP.

The fluorine content in SOP materials can be easily changed by replacing fluorinated structural blocks or changing the degree of fluorination of a given molecular structural block. Compositions of fluorinated SOPs can have hydrophobicity, and can also be specially designed to possess some second property (for example, the ability to transfer charge carriers) to create films with hybrid properties.

Fluorinated SOP can be obtained by introducing into the reaction one or more molecular structural blocks, at least one of which contains fluorine. All molecular building blocks in the reaction mixture may contain fluorine. Molecular building blocks may optionally contain another halogen, such as chlorine.

Fluorinated molecular structural blocks can be obtained from one or more structural blocks containing a carbon or silicon atomic core; structural blocks containing alkoxyl cores; structural blocks containing a nitrogen or phosphorus atomic core; structural blocks containing aryl skeletons; structural blocks containing carbonate skeletons; structural blocks containing a carbocyclic, carbobicyclic or carbotricyclic backbone; and structural blocks containing oligothiophene skeleton. Such fluorinated molecular building blocks can be obtained by replacing or replacing one or more hydrogen atoms with a fluorine atom. In one or more of the listed molecular structural blocks, all carbon-bound hydrogen atoms can be replaced by fluorine. In one or more of the listed molecular building blocks, one or more hydrogen atoms may be substituted with another halogen, such as chlorine. In addition to fluorine, SOPs may also contain other halogens.

One or more fluorinated molecular structural blocks may be contained in fluorinated SOP in an amount of from about 5 to about 100% by weight or at least about 50% by weight per 100 parts by weight of SOP.

In fluorinated SOP, more than about 20% of the H atoms can be replaced by fluorine atoms, or more than about 95% of the H atoms can be replaced by fluorine atoms, or about 100% of the H atoms can be replaced by fluorine atoms.

In fluorinated SOP, more than about 20%, or more than about 50%, or more than about 95%, or about 100% of the C-bonded H atoms can be replaced by fluorine atoms.

SOPs can also have a significant hydrogen content, for example, in the form of carbon bound hydrogen. Any desired percentage of hydrogen atoms can be selected depending on the sum of the carbon bound hydrogen and the carbon bound fluorine atoms. For example, the ratio of carbon-bound hydrogen to carbon-bound fluorine may be less than about 10, less than about 5, or less than about 0.1, or less than about 0.01.

The fluorine content of the fluorinated SOP can be from about 5% to about 75% by weight, or from about 10% to about 50% by weight. The fluorine content of some fluorinated SOPs can be at least about 10% by weight or at least about 50% by weight, and the upper limit of the fluorine content is about 75% by weight or from about 60% by weight.

In SOP, any desired number of segments can be fluorinated. The percentage of fluorine-containing segments may be more than about 10% by weight, for example more than about 30% by weight or more than 50% by weight; the upper limit of the percentage of fluorine-containing segments may be 100% or less about 70% by weight.

The fluorinated SOP described in the invention may be a “solvent resistant” SOP, SOP with capping groups, a composite SOP and / or SOP with a periodic structure. The term "solvent resistant" means the predominant absence of (1) leaching of atoms and (or) molecules that have been covalently linked to SOP and (or) a SOP composition (such as composite SOP), and (or) (2) phase separation of molecules that were part of the SOP and / or SOP composition (such as a composite SOP), which increases the susceptibility of the layer into which the SOP enters to cracking under the influence of a solvent / stress or decomposition.

At the macroscopic level, SOP can be predominantly micro-free SOP or micro-free SOP with continuous covalent organic structures, which can have a large extent, such as, for example, significantly more than one millimeter in length, for example, one meter.

“Advantageously not containing micro-holes SOP” or “not containing micro-holes SOP” can be obtained from the reaction mixture, which is applied to the surface of the underlying substrate. The term "predominantly free of micro-holes SOP" means a SOP in which per square centimeter there are mainly no micro-holes, pores or intervals greater than the distance between the cores of two adjacent segments; or in which there are less than 10 micro-holes, pores or intervals per square centimeter whose diameter exceeds about 250 nanometers. The term “micro-free SOP” means a SOP in which there are no perforations, pores or intervals per square micron greater than the distance between the cores of two adjacent segments, or in which there are no perforations per square micron, pores or intervals greater than about 500 angstroms.

Fluorinated molecular structural blocks can be obtained by fluoridation of any "source" non-fluorinated molecular structural blocks by known methods. For example, the “starting” non-fluorinated molecular building blocks can be fluorinated with elemental fluorine at elevated temperatures, such as above about 150 ° C., or other known methods to produce a mixture of fluorinated molecular building blocks with different degrees of fluorination, which may optionally be purified to obtaining individual fluorinated molecular structural blocks. Alternatively, fluorinated molecular building blocks can be synthesized and / or simply obtained by acquiring the desired fluorinated molecular building blocks. The conversion of the “starting” non-fluorinated molecular block to a fluorinated molecular block can be carried out under reaction conditions that use a single set or range of known reaction conditions, and can be a known single-step reaction or a known multi-step reaction. Examples of reactions may include one or more known reaction mechanisms, such as addition and / or exchange.

For example, converting the starting non-fluorinated molecular block to a fluorinated molecular block can include contacting the non-fluorinated molecular block with a known dehydrohalogenating agent to form a fluorinated molecular block. The dehydrohalogenation step can be carried out under conditions capable of transforming to replace at least about 50% of H atoms with fluorine atoms, or to replace more than about 95% H atoms with fluorine atoms, or to replace about 100% H atoms with fluorine atoms. The dehydrohalogenation step can be carried out under conditions capable of converting in order to replace at least about 99% of the hydrogen atoms, such as carbon bound hydrogen atoms, with fluorine. Such a reaction can be carried out in a liquid phase or a gas phase or a combination of a gas and a liquid phase, and it is provided that the reaction can be carried out periodically, continuously or using a combination of the above modes. Such a reaction may be carried out in the presence of a catalyst, such as activated carbon. Other catalysts can be used individually or in combination with each other or depending on the requirements of a particular fluorinated molecular block, including, for example, palladium-based catalysts, platinum-based catalysts, rhodium-based catalysts and ruthenium-based catalysts.

Molecular structural blocks require at least two functional groups (x≥2), while they may contain functional groups of the same type or two or more types.

The symmetry of molecular building blocks refers to the arrangement of functional groups (Fgs) around the circumference of segments of the molecular building block. The use of symmetric structural blocks is practical for two reasons: (1) the prediction of the structuring of molecular structural blocks is improved, since the arrangement of the correct figures is a more studied process in reticular chemistry, and (2) the completed reaction between molecular structural blocks is facilitated due to the smaller number of possible erroneous configurations / orientations of symmetrical building blocks that are capable of causing many layout defects within the SOP.

In FIG. 1A-P illustrate examples of building blocks with distinguished symmetrical elements. Such symmetrical elements are present in structural blocks that can be used in the present invention. The building blocks of such examples may optionally be fluorinated.

Examples of fluorinated molecular building blocks can be obtained by fluorinating building blocks containing a carbon or silicon atomic core; structural blocks containing alkoxyl cores; structural blocks containing a nitrogen or phosphorus atomic core; structural blocks containing aryl skeletons; structural blocks containing carbonate skeletons; structural blocks containing a carbocyclic, carbobicyclic or carbotricyclic backbone; and structural blocks containing oligothiophene skeleton. Such fluorinated molecular building blocks can be obtained by fluorinating a non-fluorinated molecular building block with elemental fluorine at elevated temperatures, such as above about 150 ° C., or by other known methods, or simply obtained by acquiring the desired fluorinated molecular building blocks.

Functional groups are reactive chemical components of molecular structural blocks that are involved in the chemical reaction of the arrangement of segments in the process of SOP formation. Non-limiting examples of functional groups include halogens, alcohols, ethers, ketones, carboxylic acids, esters, carbonates, amines, amides, imines, ureas, aldehydes, isocyanates, tosylates, alkenes, alkynes, and the like.

A segment is part of a molecular structural block on which functional groups are based and which contains all atoms not associated with functional groups. In addition, the composition of the molecular block structural segment remains unchanged after the formation of SOPs.

The SOP segment may contain at least one atom of an element other than carbon, for example, at least one atom selected from the group consisting of hydrogen, oxygen, nitrogen, silicon, phosphorus, selenium, fluorine, boron and sulfur.

The linker is a chemical component that is formed in SOP after a chemical reaction between functional groups contained in molecular structural blocks and / or a capping group.

The linker may be a covalent bond, a single atom, or a group of covalently bonded atoms. Linkers can be well-known chemical groups, such as, for example, esters, ketones, amides, imines, ethers, urethanes, carbonates, and the like. or their derivatives.

SOPs have any applicable aspect ratio. For example, SOPs may have ratios of geometric dimensions greater than about 30: 1 or greater than about 100: 1. The ratio of the geometric dimensions of the SOP is the ratio of its average width or diameter (next to the largest thickness) and its average thickness (smallest). The largest size is the SOP its length, which is not taken into account when calculating the ratio of the geometric dimensions of the SOP.

Fluorinated SOP can be single-layer (thickness of one segment or several segments) or multilayer (each layer thickness of one segment or several segments). "Thickness" means the smallest film size. As indicated above, SOP segments are molecular blocks covalently linked by linkers that form the molecular structure of the film. The film thickness can also be determined by the number of segments along the axis of the film in cross section. A "single layer" SOP is the simplest case when, for example, the film has a thickness of one segment. SOP, in which two or more segments are located on this axis, is called SOP of "multi-segment" thickness.

CBSs have characteristic properties, such as high heat resistance (usually above 400 ° C under atmospheric conditions), poor solubility in organic solvents (chemical stability), and porosity (the ability to reversibly absorb guest molecules). SOPs may also have these characteristic properties.

Additional functionality reflects a property that is not inherent in conventional CBS and can be obtained by choosing molecular structural blocks whose molecular compositions provide additional functionality for the resulting SOPs.

The term “predicted property” of a molecular building block means a known property of certain molecular compositions or a property that can be properly discovered by one of ordinary skill in the art after studying the molecular composition of a segment. The terms "predicted property" and "additional functionality" mean the same general property (hydrophobicity, electroactivity, etc.), but the "predicted property" is used in relation to the molecular structural unit, and the "additional functionality" in relation to SOP.

Hydrophobicity (superhydrophobicity), hydrophilicity, lipophobicity (superlipophobicity), lipophilicity, photochromia and (or) electroactivity (conductive properties, semiconducting properties, charge transfer) SOPs are some examples of properties that may reflect the "additional functionality" of SOPs.

The term hydrophobic (superhydrophobic) means the ability to repel water or other polarized particles. Hydrophobic are substances that have water contact angles greater than 90 °, measured using a goniometer or similar instrument. High hydrophobicity corresponds to water contact angles from about 130 ° to about 180 °. Superhydrophobicity corresponds to wetting angles with water above about 150 °.

One can speak of superhydrophobicity when a drop of water forms a certain angle of sliding with the surface, such as from about 1 ° to less than about 30 ° or a sliding angle of less than about 10 °.

The term hydrophilic means the ability or surface capable of attracting, absorbing, or absorbing water or other polarized particles.

The term lipophobic (oleophobic) means the ability to repel oil or other non-polarized particles, such as alkanes, fats and paraffins. Lipophobic substances have angles of contact with oil greater than 90 °, measured using a goniometer or similar device. The term oleophobic means the wettability of a surface that has a wetting angle of ink, solid ink, hexadecane, dodecane, hydrocarbons, etc., fixed under the influence of ultraviolet radiation. about 55 ° or more. High oleophobicity is indicated when a drop of a hydrocarbon-based liquid forms a large contact angle with the surface, such as from about 130 ° or from about 135 ° to about 170 °. Super oleophobicity is said when a drop of a hydrocarbon-based liquid forms a large wetting angle with the surface, such as more than 150 °.

Super oleophobicity is also indicated when a drop of a hydrocarbon-based liquid forms a slip angle with the surface from about 1 ° to less than about 30 ° or less than about 10 °.

The term lipophilic (oleophilic) means the ability to attract oil or other non-polarized particles, such as alkanes, fats and paraffins, or to a surface that is easily wetted by such particles. Lipophilic substances usually differ in that they have a wetting angle of oil from small to zero, measured using a goniometer. Lipophilicity can also be characterized by swelling of the substance under the action of hexane or other non-polar liquids.

There are various methods for measuring the contact angle or contact angle. For example, wetting can be measured as the contact angle that the base and tangent to the surface of the liquid droplet form at the contact point. In particular, the contact angle can be measured using the Fibro DAT1100. The wetting angle determines the interaction between the liquid and the base. A drop of liquid of a given volume can be automatically applied to the surface of the sample using a micropipette. The camcorder, at predetermined time intervals, receives images of the droplet in contact with the base. Methods of analysis of the obtained images determine the contact angles between the drop and the base. The rate of change of the contact angle as a function of time is calculated.

The term electroactive means the transfer property of electric charge carriers (electrons and (or) holes). Electroactive materials include conductors, semiconductors, and charge transfer materials. Conductors are defined as materials that easily carry an electric charge in the presence of a potential difference. Semiconductors are defined as materials that are not characterized by charge transfer, but which can become conductive if there is a potential difference and the applied effects are applied, such as, for example, an electric field, electromagnetic radiation, heat, etc. Carrier transfer materials are defined as materials capable of transferring a charge carrier when it is introduced from another material, such as, for example, a dye, pigment or metal in the presence of a potential difference.

Conductors can be additionally defined as materials that, when using a potentiometer, give a signal from about 0.1 to about 10 ⁷ C / cm.

Semiconductors can be additionally defined as materials that, when using a potentiometer, give a signal from about 10 ^-6 to about 10 ⁴ C / cm in the presence of effects, such as, for example, electric field, electromagnetic radiation, heat, etc. Alternatively, semiconductors can be defined as materials with the mobility of electrons and (or) holes, measured by flight time methods, in the range from 10 ^-10 to about 10 ⁶ cm ² V ^-1 s ^-1 in the presence of impacts, such as, for example , electric field, electromagnetic radiation, heat, etc.

Carrier transfer materials can be further defined as materials with electron and (or) hole mobility measured by flight time methods ranging from 10 ^-10 to about 10 ⁶ cm ² V ^-1 s ^-1 .

Fluorine-containing polymers are known to have lower surface energy than the corresponding hydrocarbon-based polymers. For example, polytetrafluoroethylene (PTFE) has lower surface energy than polyethylene (20 Mn / m and 35.3 Mn / m). The inclusion of fluorine in SOPs, in particular when fluorine is present on the film surface, can be used to modulate the surface energy of SOPs compared to the corresponding non-fluorinated SOPs. In most cases, when fluorine is included in SOPs, the surface energy of the films decreases. The degree of modulation of the surface energy of SOPs may depend, for example, on the degree of fluorination and / or structuring of fluorine on the surface of SOPs and / or inside SOPs. The degree of fluorination and / or structuring of fluorine on the surface of the SOP are parameters that can be adjusted.

Molecular structural blocks containing highly fluorinated segments have predicted hydrophobicity, and SOPs with additional hydrophobic functionality can be obtained from them. Highly fluorinated segments are segments in which the number of fluorine atoms contained in the segment (s) divided by the number of hydrogen atoms contained in the segment (s) exceeds one. From fluorinated segments that are not highly fluorinated segments, SOPs with additional hydrophobic functionality can also be obtained.

Fluorinated SOPs can be obtained from varieties of any of the molecular building blocks, segments and / or linkers in which one or more hydrogen atoms in the molecular building blocks are replaced by fluorine.

Said fluorinated segments may contain, for example, fluorinated alcohols with the general structure HOCH ₂ (CF ₂ ) _n CH ₂ OH and their corresponding dicarboxylic acids and aldehydes, in which n is an integer from 1 or more, such as from 1 to about 100 or from 1 to about 60; or from 2 to about 30; tetrafluorohydroquinone, perfluoroadipic acid hydrate, 4,4 ′ - (hexafluoroisopropylidene) diphthalic anhydride, 4,4 ′ - (hexafluoroisopropylidene) diphenol and the like.

SOPs with additional electroactive functionality can be obtained by using molecular structural blocks that have predicted electroactivity and (or) are electroactive as a result of the arrangement of conjugated segments and linkers. Molecular building blocks with a predicted hole transport ability, a predicted electron transfer ability, and predicted semiconducting properties will be described below.

A method for manufacturing fluorinated SOPs typically includes a series of operations or steps that can be performed in any applicable sequence and with the possibility of performing two or more operations simultaneously or in close proximity to time.

A method of manufacturing a structured organic film, including:

(a) obtaining a liquid-containing reaction mixture, which includes many molecular structural blocks, each of which contains a segment (at least one of which may contain fluorine) and several functional groups, and a primary SOP,

(b) applying the reaction mixture in the form of a crude film,

(c) converting the raw film containing molecular structural blocks into a dry film, which is SOP, containing many segments and many linkers forming a covalent organic structure, while at the macroscopic level, the covalent organic structure is a film,

(d) the optional separation of SOP from the base of the coating in order to obtain an independent SOP,

(e) optional roll formation from an independent SOP,

(e) optionally cutting the SOP and stapling the tape therefrom, and

(g) the optional implementation of the described method (s) of obtaining SOPs using SOPs (which was obtained by performing the described method (s) of obtaining SOPs) as the basis for the subsequent method (s) of obtaining SOPs.

The advantage of the reaction mixtures containing liquid and fluorinated SOP is their uniformity. It is known from the art that fluorinated molecules may have poor solubility in solvents. The present invention provides liquid and fluorinated SOP containing reaction mixtures in which molecular structural blocks (such as fluorinated molecular structural blocks) can optionally be dissolved, optionally using primary SOP.

The reaction mixture contains many molecular building blocks that are dissolved, suspended or mixed in a liquid. Many molecular building blocks can be of the same type or of two or more types. If one or more of the molecular building blocks is a liquid, the use of additional liquid is optional. Optionally, catalysts may be added to the reaction mixture to facilitate the production of primary SOP and / or the change in kinetics of SOP production in the above step (c). The term "primary SOP" can mean at least two molecular structural blocks that participated in the reaction and have a greater molecular weight than the original molecular structural block, and contain many functional groups that can participate in subsequent reactions with functional groups of other structural blocks or primary SOPs, as a result of which SOP is formed, which can be predominantly defect-free or defect-free SOP, and (or) activation of the molecular structural block groups for imparting increased or modified reactivity to the process of film formation.

The components of the reaction mixture (molecular building blocks, optionally liquid, optionally catalysts and optionally additives) are combined in a vessel. The order in which the components of the reaction mixture are added may vary, however, usually when a primary SOP is used in the production of SOPs or a primary SOP is formed, a catalyst may be added to the reaction mixture, if one is used, as a wet film. The reaction mixture can also be mixed, shaken, crushed, etc., to ensure uniform distribution of the components of the composition before applying the reaction mixture in the form of a crude film.

Before applying the reaction mixtures in the form of a crude film, they can be heated. This can facilitate the dissolution of one or more molecular structural blocks and / or increase the viscosity of the reaction mixture due to the partial reaction of the reaction mixture before applying the crude layer in order to form primary SOPs. For example, the weight percent in the reaction mixture of molecular building blocks that are included in the prereacted molecular building blocks of the primary SOPs may be less than 20%, such as from about 15% to about 1% or from 10% to about 5%. The molecular weight of 95% of the primary SOP molecules is less than 5000 daltons, for example 2500 daltons or 1000 daltons. The preparation of primary SOPs can be used to increase the concentration of molecular structural blocks in the reaction mixture.

In the case of the formation of primary SOPs by activating functional groups, the molar percentage concentration of activated functional groups may be less than 50%, for example, from about 30% to about 10% or from about 10% to about 5%.

Two methods for the formation of primary SOPs (the formation of primary SOPs through a reaction between molecular structural blocks or the formation of primary SOPs by activating functional groups of a molecular structural block) can be carried out in combination, while the molecular structural blocks included in the structures of primary SOPs can contain activated functional groups. The formation of primary SOPs through the reaction between molecular structural blocks and the formation of primary SOPs by activating the functional groups of the molecular structural block can be carried out simultaneously.

The duration of the formation of primary SOPs is from about 10 seconds to about 48 hours, for example, from about 30 seconds to about 12 hours, or from about 1 minute to 6 hours.

The viscosity of the reaction mixture is from about 10 to about 50,000 cP, for example, from about 25 to about 25,000 cP or from about 50 to about 1000 cP.

The concentration of molecular building blocks and capping groups in the reaction mixture is defined as the total weight of the molecular building blocks and optional capping groups and catalysts divided by the total weight of the reaction mixture. The concentration of the building blocks can be from about 3 to 100%, for example, from about 5 to about 50%, or from about 15 to about 40%. The primary SOP can consist of structural blocks with one or more additional functionalities selected from the group including additional hydrophilic functionality, additional superhydrophobic functionality, additional hydrophilic functionality, additional lipophobic functionality, additional superlipophobic functionality, additional lipophilic functionality, additional photochromic functionality and additional electroactive functionality .

The liquids used in the reaction mixture may be pure liquids, such as solvents and / or solvent mixtures. Liquids are used to dissolve or suspend molecular building blocks and catalysts / modifiers in the reaction mixture. The choice of liquid is usually made taking into account the balancing of the solubility / dispersion of the molecular building blocks and the specific concentration of the building blocks, the viscosity of the reaction mixture and the boiling point of the liquid, which affects the conversion of the crude layer to dry SOP. Applicable liquids may have a boiling point of from about 30 to about 300 ° C, such as from about 65 ° C to about 250 ° C or from about 100 ° C to about 180 ° C.

Liquids may contain various classes of molecules, such as alkanes; mixed alkanes; branched alkanes; aromatic compounds; ethers; cyclic ethers; esters; ketones; cyclic ketones; amines; amides; alcohols; nitriles; halogenated aromatic compounds; halogenated alkanes; and water.

A catalyst may optionally be present in the reaction mixture to facilitate the conversion of the crude layer to dry SOP. The selection and use of an optional catalyst depends on the functional groups of the molecular building blocks. A typical catalyst concentration is from about 0.01% to about 25%, for example from about 0.1% to about 5%, of the concentration of molecular building blocks in the reaction mixture. The catalyst may optionally be present in the final SOP composition.

Optionally, additives or auxiliary components, such as additives, may be present in the reaction mixture and the crude layer. Such additives or auxiliary components may also be included in dry SOP. The terms “additive” or “auxiliary component” mean, for example, atoms or molecules that are not bound by covalent bonds in SOP, but randomly distributed in the composition. Such additives can be used to change the physical properties of SOPs, such as electrical properties (conductivity, semiconducting properties, electron transfer, hole transfer), surface energy (hydrophobicity, hydrophilicity), tensile strength and thermal conductivity; such additives may contain elasticizers, reinforcing fibers, lubricants, antistatic agents, binders, wetting agents, antivalents, combustion inhibitors, UV stabilizers, oxidation inhibitors, biocides, dyes, pigments, perfumes, deodorants, nucleation initiators, etc.

The amount of fluoroelastomer compound present in the SOP, calculated on the total weight percentage of solids, is from about 1 to about 50%, or from about 2 to about 10% by weight of SOP. Composite SOPs may contain metal particles, when present, in any desired or effective amount, such as from about 0.25% to about 70% by weight of SOPs, or from about 1% to about 15% by weight of SOPs.

The composition may, individually or in combination, contain auxiliary components or additives, when present, in any desired or effective amount, such as from about 1% to about 50% by weight of the composition or from about 1% to about 20% by weight of the composition .

The properties of SOPs can be changed using auxiliary components (additives and additives, such as hole transport molecules (mTBD), polymers (polystyrene), nanoparticles (C60 fullerene), small molecules of organic matter (biphenyl), metal particles (copper micropowder), electron acceptors (quinone)) and fluorinated particles (polytetrafluoroethylene PTFE)) to produce composite structured organic films. Auxiliary components can be introduced into the liquid composition, which is used to obtain a crude film, which is converted into SOP. Auxiliary components (additives, additives, etc.) can be dissolved or not dissolved (suspended) in the reaction mixture.

The reaction mixture can be applied in the form of a raw film to a variety of substrates, such as the faces of the printheads, by various methods of liquid deposition.

The bases include, for example, polymers, paper, metals and metal alloys, elements of groups III-VI of the periodic table in alloyed and undoped forms, metal oxides, metal chalcogenides and pre-prepared SOPs.

The thickness of the base can be from about 10 micrometers to more than 10 millimeters, for example from about 50 to about 100 micrometers, especially in the case of a flexible base made of plastic, and from about 1 to about 10 millimeters in the case of a hard base, such as glass or silicon .

The reaction mixture can be applied to the substrate using a variety of liquid precipitation methods, including, for example, centrifugal coating, a doctor blade coating, coating the tape, dip coating, spray coating of the funnel, coating with excess strips screen printing, inkjet printing, spray coating, embossing, etc. The thickness of the crude layer may be from about 10 nm to about 5 mm, for example, from about 100 nm to about 1 mm, or from about 1 μm to about 500 μm.

After performing the described step (b), optional capping groups and / or auxiliary components may be used.

Capping groups and (or) auxiliary components can be applied uniformly or unevenly on the formed crude layer, including various patterns, while the concentration or density of the capping (their) group (s) and (or) auxiliary component is reduced in certain areas in order to form on the raw a layer of a pattern of alternating strips of a given width with high and low concentrations of the capping group (s) of the auxiliary component.

The term "conversion" refers to any applicable method that promotes the reaction of molecular structural blocks and (or) primary SOP, such as a chemical reaction of functional groups of structural blocks and (or) primary SOP. In the case where it is necessary to remove the liquid in order to obtain a dry film, “conversion” also refers to the removal of liquid. The reaction of molecular structural blocks and (or) primary SOP and the removal of liquid can occur sequentially or simultaneously. A fluid may also be one of the molecular building blocks and may be incorporated into SOPs. The term “dry SOP” means predominantly dry SOP or with a liquid content of less than about 5% by weight of SOP or with a liquid content of less than 2% by weight of SOP.

The fluorine content of the fluorinated dry SOP can be from about 5% to about 75% by weight, or from about 10% to about 50% by weight. The fluorine content in the fluorinated dry SOP is at least about 10% by weight or at least 50% by weight, and the upper limit of the fluorine content is about 75% by weight.

The conversion of the crude layer to obtain dry SOP can be carried out by any applicable method. Converting the wet layer to a dry SOP typically involves heat treatment, including, for example, oven drying, infrared (IR) drying, and the like. at temperatures from 40 to 350 ° C and from 60 to 200 ° C and from 85 to 160 ° C. The total heating time may be from about 4 seconds to about 24 hours, for example, from 1 minute to 120 minutes.

The molecular size of the auxiliary component can be selected so that during the conversion of the crude layer in order to obtain dry SOP, the auxiliary component is captured by the SOP structure, as a result of which the captured auxiliary component will not be washed out of the SOP under the influence of liquid toner or solvent.

IR conversion of the wet layer into a film with CBS can be achieved using an IR heating module mounted on a conveyor belt. Various types of IR emitters, such as carbon IR emitters or shortwave IR emitters (manufactured by Heraerus), can be used. Additional information on examples of carbon IR emitters or short-wave IR emitters is given in the following table (Table 1).

Independent SOPs can be obtained by applying the wet layer to an appropriate base with low adhesion. Suitable substrates having low adhesion to SOPs may include, for example, metal foil, metallized polymer substrates, release paper and SOPs, such as SOPs, whose surface properties have been modified to impart low adhesion or a reduced susceptibility to adhesion or attachment. The separation of SOP from the base can be carried out in various ways by a person skilled in the art. For example, the separation of the SOP from the base can be carried out starting from the corner or edge of the film, and is not necessarily facilitated by passing the base and SOP over a curved surface.

A self-contained SOP or SOP on a flexible basis may not necessarily be rolled up.

SOP can be used as a basis in the formation of SOPs in order to obtain a multilayer structured organic film. Layers of multilayer SOPs can be chemically bonded or in physical contact. Chemically bonded multilayer SOPs are formed when functional groups present on the surface of the base of SOPs are able to react with the molecular structural blocks present in the applied crude layer used to form the second layer of the structured organic film. The layers of a multilayer SOP in physical contact may not be chemically bonded to each other.

SOP can have a microscopic structured system of segments. The term “structured” means a sequence in which segments are connected to each other, for example, when segment A is connected only to segment B, and vice versa, segment B is connected only to segment A. The minimum required degree of structuring is the degree required for the formation of the film described in the invention by a method and which can be expressed in quantitative form as the formation of about 20% or more of the specified linking groups or about 40% or more of the specified linking groups; the nominal degree of structuring in the present invention is the formation of about 60% of the specified linking groups, for example, about 100% of the specified linking groups.

For testing and calculating free surface energy, the samples were cut with a two-knife cutter into rectangles of 15 mm × 50-145 mm in size. The thickness of the samples should be less than 1.5 mm when using a standard holder and less than 5.0 mm when using a special holder of their own manufacture. The sample was placed on a double-sided tape holder. Three control liquids were used to measure the contact angle: water, formamide, and diiodomethane. About 8 drops were used depending on the availability of samples, and the contact angle was measured. For 0.1 sec, 1 sec and 10 sec, the average wetting angle was measured. Using the Lewis acid base method, the free surface energy, the acidic and basic components of the polar surface energy, and the dispersive component were calculated.

For energy at the interface between solid and liquid phases, the Lewis acid base method is given by the following equation:

$${\gamma }_j\left(\mathrm{one}+\cos {\theta }_j\right)=2{\left({\gamma }_s^{LM}{\gamma }_j^{LM}\right)}^{\frac{\mathrm{one}}{2}}+2{\left({\gamma }_s^{-}{\gamma }_j^{+}\right)}^{\frac{\mathrm{one}}{2}}+2{\left({\gamma }_s^{+}{\gamma }_j^{-}\right)}^{\frac{\mathrm{one}}{2}}$$

wherein

(LW), (+), (-) mean the dispersive, acidic and basic components of the SFE coefficient,

j means liquids 1, 2, 3,

θ _j means the wetting angle of the base with a j-fold liquid,

γ _j means the surface tension of the liquid j, and

the subscript s means solid.

Example 1

Stage (a)

Obtaining a liquid containing a reaction mixture

The following was mixed: octafluoro-1,6-hexanediol [segment = octafluoro-1,6-hexyl; functional group = hydroxyl (-OH)] structural unit (0.43 g, 1.65 mmol), second N4, N4, N4 ′, N4′-tetrakis (4- (methoxymethyl) phenyl) biphenyl-4,4′- diamine [segment = N4, N4, N4 ′, N4′-tetra-p-tolylbiphenyl-4,4′-diamine; functional group = methoxy ether (-CH ₃ )] structural unit (0.55 g, 0.82 mmol), 0.05 g of acid catalyst 20% by weight of a Nacure XP-357 solution to obtain a liquid-containing reaction mixture, a leveling additive in an amount of 0.04 g. 25% by weight of a solution of Silclean 3700 and 2.96 g of 1-methoxy-2-propanol. The mixture was shaken and heated to 85 ° C for 2.5 hours, and then filtered through a 45 micron PTFE membrane.

Stage (b)

Application of the reaction mixture in the form of a crude film

The reaction mixture was applied to the reflective surface of the MYLAR ™ metallized (TiZr) substrate using a constant speed smear coating apparatus equipped with a 10 mil strip.

Stage (c)

Convert raw film to dry SOP

The metallized MYLAR ™ base layer of the wet layer was quickly transferred to an active ventilation oven preheated to 155 ° C and heated for 40 minutes. The result was an SOP with a thickness of 6-8 microns, which could be peeled off from the base in the form of an independent film. SOP had an amber color.

Example 2

Stage (a)

Obtaining a liquid containing a reaction mixture

The following was mixed: dodecafluoro-1,8-octanediol [segment = dodeca-fluoro-1,8-octyl; functional group = hydroxyl (-OH)] structural unit (0.51 g, 1.41 mmol), second N4, N4, N4 ′, N4′-tetrakis (4- (methoxymethyl) phenyl) biphenyl-4,4′- diamine [segment = N4, N4, N4 ′, N4′-tetra-p-tolylbiphenyl-4,4′-diamine; functional group = methoxy ether (-OCH ₃ )] structural unit (0.47 g, 0.71 mmol), acid catalyst in an amount of 0.05 g of a 20% by weight Nacure XP-357 solution to obtain a liquid-containing reaction mixture, leveling additive in an amount of 0.04 g of 25% by weight of Silclean 3700 and 2.96 g of 1-methoxy-2-propanol. The mixture was shaken and heated to 85 ° C for 2.5 hours, and then filtered through a 45 micron PTFE membrane.

Stage (b) as in Example 1

Stage (c) as in Example 1

The result was an SOP with a thickness of 6-8 microns, which could be peeled off from the base in the form of an independent film. SOP had an amber color.

Example 3

Stage (a)

Obtaining a liquid containing a reaction mixture

The following was mixed: hexadecafluoro-1,10-decanediol [segment = hexadecafluoro-1,10-decyl; functional group = hydroxyl (-OH)] structural unit (0.57 g, 1.23 mmol), second N4, N4, N4 ′, N4′-tetrakis (4- (methoxymethyl) phenyl) biphenyl-4,4′- diamine [segment = N4, N4, N4 ′, N4′-tetra-p-tolylbiphenyl-4,4′-diamine; functional group = methoxy ether (-CH ₃ )] structural unit (0.41 g, 0.62 mmol), an acid catalyst in an amount of 0.05 g of a 20% by weight Nacure XP-357 solution to obtain a liquid-containing reaction mixture, leveling the additive in the amount of 0.04 g of a 25% by weight solution of Silclean 3700 and 2.96 g of 1-methoxy-2-propanol. The mixture was shaken and heated to 85 ° C for 2.5 hours, and then filtered through a 45 micron PTFE membrane.

Stage (b) as in Example 1

Stage (c) as in Example 1

The result was an SOP with a thickness of 6-8 microns, which could be peeled off from the base in the form of an independent film. SOP had an amber color.

Example 4

Stage (a)

Obtaining a liquid containing a reaction mixture

The following was mixed: octafluoro-1,6-hexanediol [segment = octafluoro-1,6-hexyl; functional group = hydroxyl (-OH)] structural unit (1.98 g, 7.55 mmol), second N2, N2, N4, N4, N6, N6-hexakis (4- (methoxymethyl) -1,3,5- triazine-2,4,6-triamine [segment = N2, N2, N4, N4, N6, N6-hexakis (methyl) -1,3,5-triazine-2,4,6-triamine; functional group = methoxy ( -OMe)] structural block (0.99 g, 2.54 mmol), an acid catalyst in an amount of 0.10 g. 30% by weight of a solution of p-toluenesulfonic acid to obtain a liquid-containing reaction mixture and 6.93 g of 1.4 dioxane: The mixture was shaken and heated to 75 ° C for 1 hour, and then filtered through a 45 micron PTFE membrane.

Stage (b)

Application of the reaction mixture in the form of a crude film

The reaction mixture was applied to the reflective surface of the MYLAR ™ metallized (TiZr) substrate using a constant speed smear coating apparatus equipped with a bar with a gap of 20 mils.

Stage (c)

Convert raw film to dry SOP

The metallized MYLAR ™ base layer of the wet layer was quickly transferred to an active ventilation oven preheated to 155 ° C and heated for 40 minutes. As a result, SOPs with a thickness of 4-5 microns were obtained, which could be peeled off from the base as an independent film. SOP was transparent.

Example 5

Stage (a)

Obtaining a liquid containing a reaction mixture

The following was mixed: octafluoro-1,6-hexanediol [segment = octafluoro-1,6-hexyl; functional group = hydroxyl (-OH)] structural unit (1.49 g, 5.68 mmol), second N2, N2, N4, N4, N6, N6-hexakis (methoxymethyl) -1,3,5-triazin-2 , 4,6-triamine [segment = N2, N2, N4, N4, N6, N6-hexfis (methyl) -1,3,5-triazine-2,4,6-triamine block; functional group = methoxy (-OMe)] structural unit (1.48 g, 3.79 mmol), an acid catalyst in an amount of 0.10 g. 30% by weight of a solution of p-toluenesulfonic acid to obtain a liquid-containing reaction mixture and 6, 93 g of 1,4-dioxane. The mixture was shaken and heated to 75 ° C for 1 hour, and then filtered through a 45 micron PTFE membrane.

Stage (b) as in Example 4

Stage (c) as in Example 4

The result was an SOP with a thickness of 10-11 microns, which could be peeled off from the base in the form of an independent film. SOP was transparent.

Example 6

Stage (a)

Obtaining a liquid containing a reaction mixture

The following was mixed: dodecafluoro-1,6-octanediol [segment = dodecafluoro-1,6-octyl; functional group = hydroxyl (-OH)] structural unit (2.18 g, 8.32 mmol), second N2, N2, N4, N4, N6, N6-hexakis (methoxymethyl) -1,3,5-triazin-2 , 4,6-triamine [segment = N2, N2, N4, N4, N6, N6-hexakis (methyl) -1,3,5-triazine-2,4,6-triamine block; functional group = methoxy (-OMe)] structural unit (0.79 g, 2.02 mmol), an acid catalyst in an amount of 0.10 g. 30% by weight of a solution of p-toluenesulfonic acid to obtain a liquid-containing reaction mixture and 6, 93 g of 1,4-dioxane. The mixture was shaken and heated to 75 ° C for 1 hour, and then filtered through a 45 micron PTFE membrane.

Stage (b) as in Example 4

Stage (c) as in Example 4

As a result, SOPs with a thickness of 4-5 microns were obtained, which could be peeled off from the base as an independent film. SOP was transparent.

Example 7

Stage (a)

Obtaining a liquid containing a reaction mixture

The following was mixed: dodecafluoro-1,6-octanediol [segment = dodecafluoro-1,6-octyl; functional group = hydroxyl (-OH)] structural unit (2.18 g, 8.32 mmol), second N2, N2, N4, N4, N6, N6-hexakis (methoxymethyl) -1,3,5-triazin-2 , 4,6-triamine [segment = N2, N2, N4, N4, N6, N6-hexakis (methyl) -1,3,5-triazine-2,4,6-triamine block; functional group = methoxy (-OMe);] structural unit (0.79 g, 2.02 mmol), acid catalyst in an amount of 0.10 g. 30% by weight of a solution of p-toluenesulfonic acid to obtain a liquid-containing reaction mixture and 6.93 g of 1,4-dioxane. The mixture was shaken and heated to 75 ° C for 1 hour, and then filtered through a 45 micron PTFE membrane.

Stage (b) as in Example 4

Stage (c) as in Example 4

As a result, SOPs with a thickness of 4-5 microns were obtained, which could be peeled off from the base in the form of an independent film. SOP was transparent.

Example 8

Stage (a)

Obtaining a liquid containing a reaction mixture

The following was mixed: dodecafluoro-1,6-octanediol [segment = dodecafluoro-1,6-octyl; functional group = hydroxyl (-OH)] structural unit (0.80 g, 2.21 mmol), second (4.4 ′, 4 ″, 4 ″ ″ - (biphenyl-4,4′-diylbis (azanetriyl) ) tetrakis (benzene-4,1-diyl)) tetramethanol [segment = (4,4 ′, 4 ″, 4 ″ ″ - (biphenyl-4,4′-diylbis (azanetriyl)) tetrakis (benzene-4,1 -diyl)) tetramethyl block; functional group = hydroxyl (-OH)] structural unit (0.67 g, 1.10 mmol), an acid catalyst in an amount of 0.08 g of a 20% by weight solution of Nacure XP-357 to obtain a liquid-containing reaction mixture, a leveling additive in the amount of 0.02 g of a 25% by weight solution of Silclean 3700, 6.33 g of 1-methoxy-2-propanol and 2.11 g of cyclohexanol. The mixture was shaken and heated to 85 ° C for 2.5 hours, and then filtered through a 45 micron PTFE membrane.

Stage (b) as in Example 4

Stage (c) as in Example 4

The result was a SOP with a thickness of 5-6 microns, which could be peeled off from the base in the form of an independent film. SOP had an amber color.

Example 9

Stage (a)

The following was mixed: dodecafluoro-1,6-octanediol [segment = dodecafluoro-1,6-octyl; functional group = hydroxyl (-OH)] structural unit (0.64 g, 1.77 mmol), second (4.4 ′, 4 ″, 4 ″ ″ - (biphenyl-4,4′-diylbis (azanetriyl) ) tetrakis (benzene-4,1-diyl)) tetramethanol [segment = (4,4 ′, 4 ″, 4 ″ ″ - (biphenyl-4,4′-diylbis (azanetriyl)) tetrakis (benzene-4,1 -diyl)) tetramethyl block; functional group = hydroxyl (-OH)] building block (0.54 g, 0.89 mmol), acid catalyst in an amount of 0.06 g of a 20% by weight Nacure XP-357 solution to obtain a liquid-containing reaction mixture, a leveling additive in the amount of 0.05 g of a 25% by weight solution of Silclean 3700, 2.10 g of 1-methoxy-2-propanol and 0.70 g of cyclohexanol. The mixture was shaken and heated to 85 ° C for 2.5 hours, and then filtered through a 45 micron PTFE membrane.

Stage (b) as in Example 4

Stage (c) as in Example 4

The result was an SOP with a thickness of 6-8 microns, which could be peeled off from the base in the form of an independent film. SOP had an amber color.

High-quality films were obtained from SOPs deposited on a stainless steel and polyimide base. SOPs can be transported, sanded and deformed without damage / peeling from the base.

Table 2 provides additional details of the obtained fluorinated SOPs. Films in all cases were applied to Mylar and cured at a temperature of 155 ° C for 40 minutes.

Wetting experiments clearly show that fluorinated SOPs have noticeably higher water repellent properties than the control SOP that does not contain fluorine. Fluorinated SOPs had an initial contact angle of more than 80 °.

Claims (19)

1. Fluorinated structured organic film (SOP), including many segments, including at least segments of the first type, and many linkers, including at least linkers of the first type, forming a covalent organic structure (CBS), and representing a covalent bond, a separate atom or a group of covalently bonded atoms,
wherein at least segments of the first type contain fluorine and are selected from the group consisting of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, 2,2,3,3,4 4,5,5,6,6,7,7-dodecanofluoro-1,8-octanediol; 2,2,3,3,4,4,5,5,6,6,7,7,8,8 , 9,9-perfluorodecane-1,10-diol, (2,3,5,6-tetrafluoro-4-hydroxymethyl-phenyl) -methanol, 2,2,3,3-tetrafluoro-1,4-butanediol, 2 2,3,3,4,4-hexafluoro-1,5-pentanediol 2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluoro-1 9-nonanediol. 2. SOP according to claim 1, wherein the plurality of segments further includes fluorine-containing segments of the second type, differing in structure from segments of the first type. 3. SOP according to claim 1, wherein from about 30% by weight to about 70% by weight of the SOP segments are fluorinated. 4. SOP according to claim 1, in which the fluorine content in the SOP is from about 5% to about 65% by weight of the SOP. 5. SOP according to claim 1, in which the distribution of fluorine is structured in SOP. 6. SOP according to claim 1, in which fluorine is randomly distributed throughout the SOP. 7. SOP according to claim 1, in which fluorine is unevenly distributed over the SOP. 8. SOP according to claim 1, in which the SOP further comprises a capping group. 9. SOP according to claim 1, which is predominantly micro-free film. 10. SOP according to claim 1, which is a composite SOP. 11. SOP according to claim 1, which has additional electroactive functionality. 12. SOP according to claim 1, which is a defect-free SOP. 13. SOP according to claim 1, in which the angle of the surface of the SOP wetted with water is at least 80 degrees. 14. SOP according to claim 1, in which the presence of fluorine-containing segments modulates the surface energy of SOP. 15. A method of obtaining a fluorinated structured organic film according to claim 1, including:
(a) obtaining a liquid-containing reaction mixture comprising: a plurality of molecular building blocks comprising at least segments of the first type, and a plurality of linkers, including at least linkers of the first type, forming a covalent organic structure (CBS), and representing a covalent bond, single atom or group of covalently bonded atoms,
wherein at least segments of the first type contain fluorine and are selected from the group consisting of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, 2,2,3,3,4 4,5,5,6,6,7,7-dodecanofluoro-1,8-octanediol; 2,2,3,3,4,4,5,5,6,6,7,7,8,8 , 9,9-perfluorodecane-1,10-diol, (2,3,5,6-tetrafluoro-4-hydroxymethyl-phenyl) -methanol, 2,2,3,3-tetrafluoro-1,4-butanediol, 2 2,3,3,4,4-hexafluoro-1,5-pentanediol 2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluoro-1 9-nonanediol;
(b) applying the reaction mixture in the form of a crude film; and
(c) the conversion of the crude film with the formation of dry SOP. 16. The method of claim 15, wherein the liquid-containing reaction mixture is a homogeneous solution. 17. The method according to p. 15, where the fluorine content in dry SOP is from 5% to 65%. 18. The method according to p. 15, where from about 30% by weight to about 70% by weight of the dry SOP segments are fluorinated. 19. Fluorinated structured organic film (SOP), including many segments, including at least segments of the first type, and many linkers, including at least linkers of the first type, forming a covalent organic structure (CBS), and representing a covalent bond, a separate atom or a group of covalently bonded atoms,
wherein at least segments of the first type contain fluorine and are selected from the group consisting of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, 2,2,3,3,4 4,5,5,6,6,7,7-dodecanofluoro-1,8-octanediol; 2,2,3,3,4,4,5,5,6,6,7,7,8,8 , 9,9-perfluorodecane-1,10-diol, (2,3,5,6-tetrafluoro-4-hydroxymethyl-phenyl) -methanol, 2,2,3,3-tetrafluoro-1,4-butanediol, 2 2,3,3,4,4-hexafluoro-1,5-pentanediol 2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluoro-1 , 9-nonanediol, and
the structure of the SOP includes fluorine-containing capping groups associated with it via linkers.

Images