RU2441874C1 - Polymer on the base of poly(ferrocenyl)sylane, method of its production and the film including the polymer the base of poly(ferrocenyl)sylane - Google Patents

Abstract

FIELD: semi-conductors.

SUBSTANCE: invention refers to polymers on the base of poly(ferrocenyl)sylane used in photon semiconductor matrixes. The invention proposes celled polymer on the base of poly(ferrocenyl)sylane including repeating blocks with three types of structures, way of its manufacturing based on spatial crossing of basic polymer and binding agent and the film including the substrate and connected to it celled polymer on the base of poly(ferrocenyl)sylane.

EFFECT: proposed celled polymers have 3D structures and are produced using technological method that does not require special multistage cleaning of precursors.

12 cl, 1 dwg, 1 ex

Description

The present invention relates to polymers based on poly (ferrocenyl) silane (abbreviated as PFS), to methods for their preparation and films based on poly (ferrocenyl) silane polymers. A simplified method for producing PFS-based polymers is proposed, the implementation of which in industry will ensure a reduction in production costs. In addition, PFS-based polymers are used in photonic semiconductor arrays.

Electroactive Polymers (EAP) are polymers that can convert electrical energy into mechanical energy, or vice versa. EAP can be divided into the category of ionic EAP and the category of electrical EAP. Compounds of metals and ionic polymers, as well as conductive polymers, belong to the category of ionic EAPs. Electrical EAPs include dielectric elastomers and electrostrictive polymers. These polymers have different purposes because of their characteristics. Among these polymers, ionic metal-polymer composites are most suitable for use in displays because of their low operating voltage and relatively short response time. However, the use of ionic metal-polymer composites in a photonic crystal matrix is difficult.

When studying the current level of technology, an analysis was made of the methods for the manufacture of crosslinked EAP polymers containing organometallic fragments capable of oxidation and reduction. In this regard, monomers containing representatives of the ferrocene group are very promising for obtaining EAP with excellent operating parameters, since they are resistant to oxygen and water, and are capable of reversibly electrochemically oxidizing and reducing in various solvents.

Such monomers (strength [1] ferrocenophanes - SFP) are polymerized by ring-opening polymerization (ROP), such as thermal polymerization (TP) or polymerization using a metal complex catalyst (MCP). However, thermal polymerization requires a high temperature of 130-280 degrees and an atmosphere of inert gas, and, in addition, it does not make it possible to control the molecular weight of the polymer (see Bellas, V .; Rehahn, M. Angewandte Chemie International Edition, 2007, 46, 5082. (2) Manners, I. Organometallics 1996, 15, 1972) [1].

Anionic (AP) SFP polymerization is performed under relatively mild conditions, giving polymers with a high degree of polymerization. It makes it possible to control the molecular weight of the polymer, but at the same time requires extremely pure monomers obtained through numerous purification processes. At the same time, the polymerization of MCP using platinum compounds as a catalyst does not require high temperature and high purity monomers, which are necessary for thermal polymerization and anionic polymerization, however, this method is not effective for controlling the molecular weight of the polymer.

Currently, polymers obtained by crosslinking linear poly (ferrocenylmethylvinyl) silanes (PFMVS) and poly (ferrocenyldivinyl) silanes (PFDVS) using organic cross-linkers are widely used as electroactive polymer materials for use in creating samples of a full-color pixel based on opal structures. (binding components) as a result of radical polymerization (see, for example, Ozin, GA Angewandte Chemie International Edition, 2009, 48, 943) [2]. In this case, linear polymers PFMVS and PFDVS are pre-synthesized by AnROP anionic polymerization (see, for example, J. Am. Chem. Soc. 1996, 118, 4102) [3] from the corresponding vinyl-substituted force [1] ferrocenophanes as a result of a separate synthetic stage. Various organic α, ω-dithiols, for example 1,4-butanedithiol, are used as a crosslinking agent in an amount of 5-10 mol% of the amount of a linear polymer. The crosslinking reaction is initiated by the radical Igracure catalyst under the influence of intense UV radiation for 10-14 hours. A crosslinked polymer sample obtained using 10 mol% cross-linker shows mechanical stability sufficient to be used as a working material in samples of full-color pixels. Despite the fact that the known method [2] for producing a crosslinked electroactive PFS polymer is relatively simple and has already proven effective for the preparation of polymer matrices of the “inverted opal” type, this method has several disadvantages. In particular:

a) the preparation of the linear polymer PFMVS or PFDVS by AnROP is a separate synthetic step, requiring the use of the original

the strength [1] of ferrocenophane of especially high purity, which underwent a special multi-stage purification (10-15 stages), and the isolation of the product from the reaction mixture — all this complicates the technological implementation of the method in industry;

b) the use of 10 mol% of an organic crosslinking agent reduces by the same amount the number of electroactive fragments in the final crosslinked polymer and, accordingly, the magnitude of its response (for example, the degree of swelling) under the influence of an electric current;

c) the crosslinking method based on the radical thiolene reaction, which requires constant exposure to powerful UV radiation to proceed, is a serious limitation of the method because it does not allow using it to obtain a crosslinked PFS polymer in the preparation of composite materials that are opaque to UV radiation. In addition, in the case of PFS polymers that are sufficiently sensitive to air oxygen, it is desirable (especially for thin PFS films) to use an inert atmosphere during the crosslinking process, which is also technologically inconvenient when continuous exposure of the sample to UV light is applied.

In general, the currently known method for the preparation of cross-linked PFS polymers suffers both from technological shortcomings (the need for special post-treatment of the initial strength [1] of ferrocenophanes, the use of special quartz equipment for UV irradiation), and the inability to achieve some technical characteristics (maximum number of electroactive ferrocene fragments in a crosslinked polymer), and in some cases it is simply unsuitable (for materials opaque to the UV range intended for impregnation of PFS-polymer ).

The problem to which the invention is directed is the development of a technologically simple way to obtain a cross-linked PFS-polymer, devoid of the disadvantages of known analogues, in particular not requiring special multi-stage methods for purification of the starting reagents (strength [1] of ferrocenophanes); consisting almost entirely of electroactive ferrocenylsilane units and suitable for producing a crosslinked PFS polymer on / in any (transparent and opaque) materials.

The technical result is achieved through the development of a new formula of cellular polymers based on PFS, which are manufactured using a simplified process and are used for the production of films, including cellular polymers based on PFS. In this case, the inventive cellular polymer based on poly (ferrocenyl) silane includes a repeating unit represented by Formula 1, a repeating unit represented by Formula 2, and a repeating unit represented by Formula 3:

<Formula 1>

<Formula 2>

<Formula 3>

where Fc is a ferrocene group represented by Formula 4a, DFc is a linker group based on diferrocenylsilane represented by Formula 4b, am ₁ and m ₂ - each individually is a number 0 or 1;

<Formula 4a>

where m4 is a number from the range from 1 to 10;

<Formula 4b>

where n ₁ and n ₂ are each individually a number from the range from 5 to 95, X ₁ is

или

or

where R ₁ and R ₂ each individually represents a substituted or unsubstituted alkyl group in the range from C6 to C20 or a substituted or unsubstituted aryl group in the range from C6 to C30, and X ₂ represents

-O-, -S-, in the range from C6 to C20 a substituted or unsubstituted alkylene group, or in the range from C6 to C30 a substituted or unsubstituted arylene group. In this case, the various options described below for the chemical formula of the inventive polymer based on PFS are possible.

A method for producing a cellular polymer based on poly (ferrocenyl) silane is also proposed, which includes the following operations: the base polymer represented by Formula 5 and the binder component represented by Formula 6 are spatially crosslinked:

<Formula 5>

where n ₁ and n ₂ each individually is a number from the range from 5 to 95, m3 is 0 or 1,

или

or

where R ₁ and R ₂ - each individually represents a substituted or unsubstituted from C6 to C20 alkyl group or a substituted or unsubstituted from C6 to C30 aryl group, and X ₂ - represents-O-, -S-, C6 to C20 substituted or an unsubstituted alkylene group, or from C6 to C30 a substituted or unsubstituted arylene group;

<Formula 6>

where n ₃ is a number from 10 to 25, and R ₃ denotes a methyl group and a ferrocenyl group represented by Formula 13, and when the methyl group and the ferrocenyl group coexist as R ₃ , the ratio of the number of methyl groups to the sum of methyl groups and ferrocenyl groups is range from 0.1 to 0.9:

<Formula 13>

where m4 is a number from 1 to 10.

And finally, the proposed structure of a polymer film, including: a substrate; and a cellular polymer based on poly (ferrocenyl) silane obtained by any of the claimed methods, characterized in that the cellular polymer based on poly (ferrocenyl) silane is bonded to this substrate.

Additional aspects of this complex of inventions related by a single concept are explained further in the text of the description using examples of implementation with reference to graphic materials. Moreover, the proposed embodiments may take various forms and should not be construed as being limited by the present description. Therefore, such embodiments are described below with reference to the drawings merely for the purpose of explaining certain aspects of the technical solution.

The PFS-based cellular polymer obtained according to the claimed invention is electroactive and cross-linked, while it includes a repeating unit represented by Formula 1, a repeating unit represented by Formula 2, and a repeating unit represented by Formula 3:

<Formula 1>

<Formula 2>

<Formula 3>

where Fc is the ferrocene group represented by Formula 4a, DFc is the linker group based on diferrocenylsilane represented by Formula 4b, and m1 and m2 are each individually 0 or 1;

<Formula 4a>

where m4 is a number from the range from 1 to 10;

<Formula 4b>

where n ₁ and n ₂ - each individually is a number from the range from 5 to 95, X ₁ is

или

or

where R ₁ and R ₂ - each individually represents a substituted or unsubstituted from C6 to C20 alkyl group or a substituted or unsubstituted from C6 to C30 aryl group, and X ₂ - represents-O-, -S-, C6 to C20 substituted or an unsubstituted alkylene group, or from C6 to C30 a substituted or unsubstituted arylene group.

According to the claimed invention, in a cellular polymer, the repeating unit of Formula 1 may have a degree of polymerization, for example, from close to 5 to close to one hundred, the repeating unit of Formula 2 may have a polymerization degree, for example, from close to five to close to one hundred, and the repeating unit of Formula 3 may have a degree of polymerization, for example, from close to ten to close to twenty-five.

According to the claimed invention, if the repeating block of Formula 1 is repeated, then at least one of the repeating blocks of Formula 2 and the repeating block of Formula 3 can be inserted between the repeating blocks of Formula 1.

A PFS-based cellular polymer including a repeating unit represented by Formula 1, a repeating unit represented by Formula 2, and a repeating unit represented by Formula 3 can be obtained by polymerizing a base polymer represented by Formula 5 and a binder component represented by Formula 6:

<Formula 5>

where n ₁ and n ₂ each individually is a number from the range from 5 to 95, m3 is 0 or 1, X ₁ is

или

or

where R ₁ and R ₂ - each individually represents a substituted or unsubstituted from C6 to C20 alkyl group or a substituted or unsubstituted from C6 to C30 aryl group, and X ₂ - represents-O-, -S-, C6 to C20 substituted or an unsubstituted alkylene group, or from C6 to C30 a substituted or unsubstituted arylene group;

<Formula 6>

where n ₃ is a number from 10 to 25, and R ₃ can denote a methyl and ferrocenyl group represented by Formula 13, and when R ₃ is a mixture of methyl and ferrocenyl groups, the molar ratio of metal to total methyl and ferrocenyl groups is in the range from 0, 1 to 0.9:

<Formula 13>

where m4 is a number from 1 to 10.

The polymers obtained according to the claimed implementation examples may include various repeating blocks in their framework, and although these repeating blocks are described as a separate formation in the composition of the polymers, such polymers can also be block copolymers or random copolymers.

As for the base polymer according to Formula 5, when m3 is 0, the base polymer may be a base polymer represented by Formula 7:

<Formula 7>

where n ₁ and n ₂ are each individually a number from the range from 5 to 95, X ₁ is

или

or

where R ₁ and R ₂ - each individually represents a substituted or unsubstituted from C6 to C20 alkyl group or a substituted or unsubstituted from C6 to C30 aryl group, and X ₂ - represents-O-, -S-, C6 to C20 substituted or an unsubstituted alkylene group, or from C6 to C30 a substituted or unsubstituted arylene group.

- Getting the base polymer

The base polymer represented by Formula 7 can be obtained according to Reaction Scheme 1:

<Reaction Scheme 1>

или

where X ₁ is

or

where R ₁ and R ₂ - each individually represents a substituted or unsubstituted from C6 to C20 alkyl group or a substituted or unsubstituted from C6 to C30 aryl group, and X ₂ - represents-O-, -S-, C6 to C20 substituted or an unsubstituted alkylene group, or from C6 to C30 a substituted or unsubstituted arylene group; n ₁ and n ₂ are each individually represented by a number from 5 to 95, and n represents n ₁ + n ₂ .

The production method according to Reaction Scheme 1 is a method for producing a linear base PFS. According to Reaction Scheme 1, the dihydrosilane-based component of Formula 8 reacts with dimethylsil [1] by ferrocenophane of Formula 9 to form a linear oligoferrocenylsilane with Formula 10 having Si-H at both ends of the chain as a result of ring opening (ROP); and then excess tetravinylsilane is added thereto to form oligoferrocenylsilane by Formula 7 hydrosilylation, carrying trivinylsilyl groups at the ends of the chain. As for the base polymer according to Formula 7, the value of the sum of n ₁ and n ₂ can lie in the range of values from close to ten to close to one hundred.

Cycle opening polymerization and hydrosilylation according to the Scheme of Reaction 1 can take place in the presence of a catalyst based on platinum (Pt) compounds, for example, Carsted catalyst Pt [(СН ₂ = СН-SiMe ₂ ) ₂ O] _1.5 and Zeiss salt dimer Pt [(С ₂ H ₄ ) Cl ₂ ] ₂ . The amount of such a platinum catalyst may range from close to 0.01 mol% to close to 1 mol%, based on 1 mol of reagent.

Hydrosilylation can be performed 2 to 10 times faster if Si (vinyl) _{4 is} taken in excess, while an excess of unreacted Si (vinyl) ₄ can be removed by vacuum.

As for Reaction Scheme 1, benzene, toluene, or xylene can be used as the organic solvent, and the reaction can be performed, for example, within 1-48 hours at a temperature of from 10 to 50 ° C.

Further, the base polymer according to Formula 7 can react with a linear oligoferrocenylsilane according to Formula 10 in the presence of a catalyst based on platinum compounds, resulting in a base polymer according to Formula 11 below, that is, the base polymer represented by Formula 5 with m3 equal to one.

<Formula 11>

where X ₁ is

или

or

where R ₁ and R ₂ - each individually represents a substituted or unsubstituted from C6 to C20 alkyl group or a substituted or unsubstituted from C6 to C30 aryl group, and X ₂ - represents-O-, -S-, C6 to C20 substituted or an unsubstituted alkylene group, or from C6 to C30 a substituted or unsubstituted arylene group; n ₁ and n ₂ - each individually represented by a number from 5 to 95.

- Obtaining a binder component

The binder component according to Formula 6, which should react with the base polymer with Formula 5, can be obtained according to Reaction Scheme 2:

<Reaction Scheme 2>

wherein as R ₄ may apply a mixture of hydrogen and a methyl group as R ₃ can be a mixture of methyl group and ferrocenyl group of Formula 13, wherein n assumes the value ₃ in the range of ten to twenty-five,

<Formula 13>

where m4 takes a value from a range of one to ten.

Reaction Scheme 2 is a process for preparing a binder component with Formula 6. In Reaction Scheme 2, poly (dimethylsiloxane) with Formula 12, which is a linear oligomer, enters into reaction with dimethylsil [1] ferrocenophane with Formula 9 in the presence of a Pt-based catalyst, to obtain thus a binder component with Formula 7.

When using poly (dimethylsiloxane) with Formula 12 as starting material, some methyl groups in it are replaced by hydrogen, and it is necessary to replace these hydrogen atoms with ferrocenyl groups with Formula 13. In other words, in poly (dimethylsiloxane) with Formula 12, R ₄ may mean a mixture of a methyl group and hydrogen, and the content of hydride groups to metal, that is, H / (H + methyl), can lie in the range from 0.1 to 0.9, for example, about 0.1-0.5, and if this value is 0.5, it means that the hydride and the methyl group in the R ₄ pres tvuyut in the ratio of 1: 1.

R ₄ can be represented by a mixture of hydrogen atoms and a methyl group, and the hydrogen in R _{4 is} replaced by a ferrocene fragment with Formula 13 according to Reaction Scheme 2. That is, in the binder component of Formula 6, R ₃ can be represented by a mixture of hydrogen and a ferrocene group with Formula 13, and the proportion of the ferrocenyl group may be the same as the hydrogen content in R ₄ . That is, when R ₄ is represented by hydrogen and a methyl group in a ratio of 1: 1, in R _{3 the} ratio between the methyl group and the ferrocenyl group can be close to 1: 1.

Reaction Scheme 3 is a particular example of Reaction Scheme 2 when R ₄ is a 1: 1 mixture of hydrogen and methyl group.

<Reaction Scheme 3>

where R ₄ includes a methyl group and hydrogen in a ratio of 1: 1, and n ₃ is a number from the range from 10 to 25, and each element m ₄ is a number from the range from 1 to 10.

In the above Reaction Scheme 3, R ₄ includes a methyl group or hydrogen in a 1: 1 ratio, and dimethylsil [1] ferrocenophan with Formula 9 is replaced with hydrogen to produce a binder component with Formula 14 containing a methyl group and a ferrocenyl group in a 1: 1 ratio.

As for Reaction Scheme 2, the organic solvent used may be benzene, toluene, or xylene, and the reaction may be carried out for 1-48 hours at a temperature of 10-50 ° C.

Reaction Scheme 2 can be carried out in the presence of a platinum-based catalyst, and such a catalyst can be, for example, a Carsted catalyst Pt [(CH ₂ = CH-SiMe ₂ ) ₂ O] _1.5 or a Zeiss salt dimer Pt [(C ₂ H ₄ ) Cl ₂ ] ₂ . The amount of platinum-based catalyst may range from close to 0.01 mol% to close to 1 mol% based on 1 mol of reagent.

- Obtaining a cellular polymer based on PFS

After the base polymer and the binder component are obtained by the above method, they react with each other according to the Reaction Scheme 4 below in the presence of a catalyst based on platinum compounds, forming a cellular polymer based on PFS:

<Reaction Scheme 4>

where X ₁ is

или

or

where R ₁ and R ₂ - each individually represents a substituted or unsubstituted from C6 to C20 alkyl group or a substituted or unsubstituted from C6 to C30 aryl group, and X ₂ - represents-O-, -S-, C6 to C20 substituted or an unsubstituted alkylene group, or from C6 to C30 a substituted or unsubstituted arylene group;

n ₁ and n ₂ are each individually many 5-95, and

m3 is the number 0 or 1.

In Reaction Scheme 4, a methyl group and a ferrocenyl group with Formula 13 below can be simultaneously present in R ₃ , and n ₃ is a number in the range of ten to twenty-five:

<Formula 13>

where m4 is a number in the range from one to ten.

In Reaction Scheme 4, one of the vinyl groups at one end of the chain of the base polymer with Formula 5 is cross-linked to the hydrogen atom at the end of the chain of the ferrocenyl group of the binder with Formula 6. That is, the base polymer with Formula 5 is not spatially crosslinked with R ₃ , which is bound with a silicon atom in the binder component of Formula 6 when R ₃ is a methyl group, and is crosslinked with R ₃ when R ₃ is a ferrocenyl group.

The PFS-based cellular polymer obtained by the spatial crosslinking reaction described above includes a repeating unit with Formula 1, a repeating unit with Formula 2, and a repeating unit with Formula 3:

<Formula 1>

<Formula 2>

<Formula 3>

where Fc is a ferrocenyl group with Formula 4a below, DFc is a linker group based on diferrocenylsilane with Formula 4b below, a m1 and m2 are each individually a number 0 or 1;

<Formula 4a>

where m4 is a number from the range from 1 to 10;

<Formula 4b>

where n ₁ and n ₂ are each individually a number from the range from 5 to 95, X ₁ is

или

or

where R ₁ and R ₂ - each individually represents a substituted or unsubstituted from C6 to C20 alkyl group or a substituted or unsubstituted from C6 to C30 aryl group, and X ₂ - represents-O-, -S-, C6 to C20 substituted or an unsubstituted alkylene group, or from C6 to C30 a substituted or unsubstituted arylene group.

The repeating unit with Formula 1 refers to the case when the vinyl groups, all located at the ends of the main polymer chain with Formula 5, are connected to the binder component with Formula 6, the repeating unit with Formula 2 refers to the case when only the vinyl group at the end of the polymer chain with Formula 5 is associated with a binder component with Formula 6, and the repeating unit with Formula 3 refers to that part of the binder component that is not associated with the base polymer.

As for Reaction Scheme 4, the organic solvent used may be benzene, toluene, or xylene, and the reaction may be carried out, for example, within 1-48 hours at a temperature of 30-80 ° C.

The reaction scheme 4 can be carried out in the presence of a catalyst based on platinum compounds, and such a catalyst can be, for example, a Carsted catalyst Pt (CH ₂ = CH-SiMe ₂ ) ₂ O] _1.5 or a dimer of the Zeise salt Pt [(C ₂ H ₄ ) Cl ₂ ] ₂ . The amount of platinum-based catalyst may range from close to 0.01 mol% to close to 1 mol%, based on 1 mol of reagent.

The PFS-based cellular polymer according to the claimed invention is a cellular structure including repeating blocks with Formulas 1, 2 and 3, wherein the cellular structure is not linear, but has a spatial character, and in it the base polymer is voluminously bonded to the binder component.

For example, a repeating block with Formula 1 can be repeated in the form of a ladder, forming a polymer in the form of a ladder, and repeating blocks with Formulas 2 and 3 are inserted into the spaces between them.

An example of a cellular polymer based on PFS, including repeating blocks with Formulas 1, 2 and 3, is represented by Formula 15:

<Formula 15>

where A is

As shown in Formula 15, the PFS-based cellular polymer is not a simple linear structure, but is characterized by a spatial (three-dimensional) structure, and the base polymer with Formula 5 is bonded to the binder component with Formula 6 in a mono- or bententate type.

Repeating blocks with Formulas 1, 2, and 3 in Formula 15 are outlined in the Formula 16 below:

<Formula 16>

where A is

With regard to Formula 16, and is an example of the recurring unit of Formula 1, b is an example of the repeating unit of Formula 2, and - an example of a repeating unit of Formula 3.

- PFS based polymer film manufacturing

The above-described PFS-based cellular polymer can be used to make films by various methods, for example, spin-coating, dip-coating, or sovent-casting on various substrates, for example glass substrates, substrates from indium and tin oxides (ITO), or plastic substrates.

This cellular polymer based on poly (ferrocenyl) silane can be synthesized by using only one type of force [1] ferrocenophane as starting material instead of several different

the strength [1] of ferrocenophanes, while the production processes are not demanding for a high degree of purification, and therefore the desired level of purification is easily achieved by using only three to four recrystallization processes. In addition, properties of the base polymer, such as chain length and the number of vinylsilyl functional groups capable of binding, can be easily controlled by using the ratio of the initial components of the strength [1] of ferrocenophan, dihydrosilane and tetravinyl silane. In addition, the binder component is easily saturated with the ferrocene group, thus, allowing to increase the number of electrochemically active fragments in the final three-dimensional cellular polymer based on PFS.

In addition, the base polymer and the binder component can be used without isolation from the reaction mixture (in situ). Since the platinum catalyst (a catalyst based on Pt compounds) in an amount of 0.02 to 0.5 mol% based on one Si-H group is used in all processes and retains its activity from the moment it is introduced at the initial stage, there is no need for multiple adding a platinum catalyst in subsequent steps.

In addition, the curing process to obtain the final product does not require ultraviolet irradiation and an inert atmosphere and can be completely performed at a temperature of 50-70 ° C in just a few hours.

Since the base polymer and the binder component necessary to obtain a cellular polymer are used as needed, even when the base polymer and binder component are prepared in advance and stored, they can be stored without compromising on quality.

As described above, a PES-based cellular polymer is easy to manufacture in large quantities (in mass production) and used as an active component of a controlled photonic semiconductor. In addition, a PES-based cellular polymer can be used in a transparent actuator or biosensor, or as an antioxidant material of a transparent electrode.

Since the content of electroactive ferrocene groups capable of reversible oxidation and reduction, as well as the cross-linking density in cellular PFS are easily controlled over a wide range during polymer preparation and can reach high values, it becomes possible to manufacture display devices based on photonic crystals with a high response speed ( short response time), a wide color range and high wear resistance, which meets the needs of consumers.

Further, the claimed invention is described in detail for options for its implementation. However, the claimed invention is not limited to the described options.

Example 1

a) Obtaining a binder component

Hydrogenated Poly (dimethylsiloxane) Me [(HSiMeO) (SiMe ₂ O)] ₆ SiMe ₃ (65 mg, 0.4 mmol, Si-H) and [Pt (C ₂ H ₄ ) Cl ₂ ] ₂ (10 mg, 0 , 8 ml, 1 mol.%) Were added to a solution of FcSiMe ₂ (200 mg, 0.8 mmol) in 1.2 ml of benzene at a temperature of 25 ° C, and stirred for 3-5 hours. Molecular weight

Me [(RSiMeO) (SiMe ₂ O)] ₆ SiMe ₃ (R = - (FcSiMe ₂ ) ₂ H) as a binder component was approximately 3800, and the content of ferrocene groups was approximately 75% (content = ferrocenyl group / (methyl group + ferrocenyl group) 100).

b) Preparation of base polymer: poly (ferrocenyl) silane with trivinylsilyl end groups

Carstead's catalyst (Aldrich, 2% Pt in xylene, 5 μl%, 0.43 mol% for Ph ₂ SiH ₂ ) was added to a solution of dimethylsil [1] ferrocenophan (0.24 g, 1.00 mmol) and diphenylsilane Ph ₂ SiH ₂ (19 μl, 0.10 mmol) in 3 ml of benzene at a temperature of 25 ° C with stirring, the reaction was carried out for 1-3 hours. The resulting product was identified using nuclear magnetic resonance (NMR).

1 H NMR (δ, CDCl ₃ ): 7.57-7.64 (o-H, Ph, 4H); 7.35-7.41 (m-H and p-H, Ph, 6H); 3.9-4.3 (C ₅ H ₄ , Fc, 77H), 0.25-0.55 (SiMe2, 58H); 5.44 (Ph2Si-H, 0.20.7H); 4.42 (Me2Si-H, 1.31.8H).

Tetravinyl silane (340 μl, 2 mmol, 10-fold excess) was added to the prepared solution, and the reaction mixture was stirred for 3 days, then the solvent was removed and the residue was dried in vacuo.

1H NMR (δ, CDCl ₃ ): 7.50-7.62 (o-H, Ph, 4H); 7.32-7.40 (m-H and p-H, Ph, 6H); 3.8-4.3 (C ₅ H ₄ , Fc, 77H), 0.25-0.55 (SiMe ₂ + CH ₂ , 64H); 5.7-5.8 (Vinyl, 5H); 6.0-6.2 (Vinyl, 10H).

c) Preparation of three-dimensional polyhydroferrocenylsilane

Carstead's catalyst (Aldrich, 2% Pt in xylene, 3 μl, 0.26 μmol Pt, 0.25 mol% on Si-H) was added to 0.26 g (1.1 mmol) of dimethylsil [1] ferrocenophan and 0.087 g (0.09 mmol) of polyhydrosiloxane ( Me ₃ Si - [(OSiMeH) (OSiMe ₂ ) ₆ ] ₃ -H) dissolved in 3 ml of benzene, the reaction mixture was stirred for 3 hours, then the solvent was removed and the residue was dried in vacuo.

1H NMR (δ, CDCl ₃ ): 4.7 (singlet, FcSiMe ₂ H, 5H), 4.0-4.2 (C ₅ H ₄ , Fc, 8H), 0.3-0.7 (Me, OSiMe ₂ + OSiMeFc + SiMe ₂ Fc + SiMe ₃ , 11H).

d) Obtaining a PFS film

The reaction products obtained according to b) and c) were mixed and then kept at room temperature for one day. Then the mixture was spin-coated on a glass substrate, and then heated for 3-12 hours at a temperature of 70 ° C, thus forming a transparent yellow-orange glassy coating.

The characteristics of the film obtained in Example 1 in terms of electrical properties during the experimental verification were determined by the method of cyclic voltometry, and the results are presented in Figure 1, where it can be verified that the oxidation and reduction processes are reversible.

As described above, according to one or more embodiments of the claimed invention, the production of a cellular polymer based on poly (ferrocenyl) silane using a simplified process, the use of a catalyst based on platinum compounds in the preparation of a base polymer, a binder component and a PFS based cellular polymer by crosslinking the base polymer and a binder component allow the reaction to be carried out in situ, while the intermediate products do not need to be purified, and the crosslinking process, which is the final step it is carried out under mild conditions, namely heat.

In addition, in the case where the cellular polymer is used to form a three-dimensional polymer film, the substrate on which the film is to be applied can be functionalized with compounds with vinyl groups, to which a binder component can then be attached. Using this operation ensures the absence of the use of excess PFS, a minimal decrease in optical characteristics is achieved, while the basic parameters of the film are improved.

It should be noted that the examples of implementation described in the description should be considered only as an illustration, but they are not restrictive. Descriptions of the characteristics or features of each embodiment of the invention should, as a rule, be considered as the basis for other similar modifications of features and aspects in various embodiments of the inventions.

Claims (12)

1. A cellular polymer based on poly (ferrocenyl) silane, including a repeating unit represented by Formula 1, a repeating unit represented by Formula 2, and a repeating unit represented by Formula 3:
<Formula 1>

<Formula 2>

<Formula 3>

where Fc is a ferrocene group represented by Formula 4a, DFc is a linker group based on diferrocenylsilane represented by Formula 4b, a m1 and m2 each individually is a number 0 or 1;
<formula 4a>

where m4 is a number from the range from 1 to 10;
<Formula 4b>

where n ₁ and n ₂ are each individually a number from the range from 5 to 95, X ₁ is

or

where R ₁ and R ₂ each individually represents a substituted or unsubstituted in the range from C6 to C20 alkyl group or substituted or unsubstituted in the range from C6 to C30 an aryl group, and X ₂ represents O-, -S-, in the range from C6 to C20 substituted or unsubstituted alkylene group, or in the range from C6 to C30 substituted or unsubstituted arylene group. 2. The cellular polymer based on poly (ferrocenyl) silane according to claim 1, characterized in that the repeating unit with Formula 1 has a polymerization degree in the range from 5 to 100, the repeating unit with Formula 2 has a polymerization degree in the range from 5 to 100, and the repeating unit with Formula 3 has a degree of polymerization in the range from 10 to 25. 3. The cellular polymer based on poly (ferrocenyl) silane according to claim 1, characterized in that at least one repeating unit with Formula 2 and one repeating unit with Formula 3 are inserted between the repeating units with Formula 1. 4. The method of producing a cellular polymer based on poly (ferrocenyl) silane according to claim 1, which includes performing the following operations: spatially crosslink the base polymer represented by Formula 5 and the binder component represented by Formula 6:
<Formula 5>

where n ₁ and n ₂ each individually is a number from the range from 5 to 95, m3 is 0 or 1, X ₁ is

or

where R ₁ and R ₂ each individually represents a substituted or unsubstituted from C6 to C20 alkyl group or a substituted or unsubstituted from C6 to C30 aryl group, and X ₂ represents —O—, —S—, from C6 to C20 substituted or an unsubstituted alkylene group, or from C6 to C30 a substituted or unsubstituted arylene group;
<Formula 6>

where n ₃ represents a number from 10 to 25, and R ₃ denotes a methyl group and a ferrocenyl group represented by Formula 13, and when the methyl group and the ferrocenyl group coexist as R ₃ , the ratio of the number of methyl groups to the sum of methyl groups and ferrocenyl groups is in the range from 0.1 to 0.9:
<Formula 13>

where m4 is a number from 1 to 10. 5. The method according to claim 4, characterized in that in the base polymer represented by Formula 5, m3 has a value of 0, and it is a base polymer represented by Formula 7:
<Formula 7>

where n ₁ and n ₂ are each individually a number from the range from 5 to 95, X ₁ is

or

where R ₁ and R ₂ each individually represents a substituted or unsubstituted from C6 to C20 alkyl group or a substituted or unsubstituted from C6 to C30 aryl group, and X ₂ represents —O—, —S—, from C6 to C20 substituted or unsubstituted alkylene group; or from C6 to C30 substituted or unsubstituted arylene group. 6. The method according to claim 5, characterized in that the method further includes:
- carrying out the reaction of dihydrosilane represented by Formula 8 with dimethylsil [1] ferrocenophan represented by Formula 9 in the presence of a catalyst based on platinum compounds, resulting in a linear oligoferrocenylsilane represented by Formula 10 having Si-H at both ends of the chain, and
- the reaction of linear oligoferrocenylsilane with tetravinylsilane to obtain a base polymer with Formula 7:

where X ₁ is

or

where R ₁ and R ₂ each individually represents a substituted or unsubstituted from C6 to C20 alkyl group or a substituted or unsubstituted from C6 to C30 aryl group, and X ₂ represents —O—, —S—, from C6 to C20 substituted or unsubstituted alkylene group, or from C6 to C30 substituted or unsubstituted arylene group; n ₁ and n _{2 are} each individually represented by a number from 5 to 95, and n represents n ₁ + n ₂ . 7. The method according to claim 6, characterized in that the method further comprises the following steps:
- carrying out the reaction of the base polymer represented by Formula 7 with a linear oligoferrocenylsilane represented by Formula 10 in the presence of a catalyst based on platinum compounds to obtain the base polymer represented by the following Formula 11:
<Formula 11>

where X ₁ is

or

where R ₁ and R ₂ each individually represents a substituted or unsubstituted from C6 to C20 alkyl group or a substituted or unsubstituted from C6 to C30 aryl group, and X ₂ - represents-O-, -S-, from C6 to C20 substituted or an unsubstituted alkylene group, or from C6 to C30 a substituted or unsubstituted arylene group; n ₁ and n _{2 are} each individually represented by a number from 5 to 95. 8. The method according to claim 4, characterized in that the binder component with Formula 6 is obtained by reacting the poly (dimethylsiloxane) represented by Formula 12 below as a linear oligomer with dimethylsil [1] ferrocenophane represented by Formula 9 in the presence of a catalyst on based platinum compounds:

wherein as R _4, a mixture of hydrogen and a methyl group as R _3, a mixture of a methyl group and ferrocenyl group of Formula 13, wherein n assumes the value ₃ in the range of ten to twenty-five,
<Formula 13>

where m4 takes a value from a range of one to ten. 9. The method according to claim 8, characterized in that R ₄ in the poly (dimethylsiloxane) represented by Formula 12 is a methyl group or a hydrogen atom, wherein the substitution ratio of the hydrogen atom to the methyl group, i.e. H / (H + methyl) ranges from 0.1 to 0.9. 10. The method according to claim 8, characterized in that in the binder component with Formula 6, R ₃ is a mixture of a metal group and a ferrocenyl group with Formula 13, and the proportion of the ferrocenyl group is in the range from 0.1 to 0.9. 11. The method according to claim 4, characterized in that the cellular polymer based on poly (ferrocenyl) silane includes a repeating unit represented by Formula 1, a repeating unit represented by Formula 2, and a repeating unit represented by Formula 3:
<Formula 1>

<Formula 2>

<Formula 3>

where Fc is a ferrocene group represented by Formula 4a, DFc is a linker group based on diferrocenylsilane represented by Formula 4b, and m1 and m2 are each individually a number 0 or 1;
<Formula 4a>

where m4 is a number from the range from 1 to 10;
<Formula 4b>

where n ₁ and n ₂ are each individually a number from the range from 5 to 95, X ₁ is

or

where R ₁ and R ₂ each individually represents a substituted or unsubstituted alkyl group in the range from C6 to C20 or a substituted or unsubstituted aryl group in the range from C6 to C30, and X ₂ represents —O—, —S—, in the range from C6 to C20 a substituted or unsubstituted alkylene group, or in the range from C6 to C30 a substituted or unsubstituted arylene group. 12. A polymer film comprising a substrate and a poly (ferrocenyl) silane-based cellular polymer according to any one of claims 1 to 3, characterized in that the poly (ferrocenyl) silane-based cellular polymer is bonded to this substrate.

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