KR101750399B1 - Poly(ferrocenyl)silane based polymer, process for preparing the same and film comprising the polymer - Google Patents

Abstract

There is provided a poly (ferrocenyl) silane network polymer, a process for producing the same, and the polymer containing film, wherein the network polymer has a three-dimensional structure and can be produced by a simplified process.

Description

The present invention relates to a poly (ferrocenyl) silane based polymer, a process for preparing the same, and a process for preparing the same,

The present invention relates to a poly (ferrocenyl) silane-based polymer, a process for producing the same, and a polymer-containing film. The polymer can be produced by a simplified process and thus can be economically advantageous and can be used for a photonic crystal matrix.

Electroactive polymer (EAP) is a polymeric material capable of converting electrical energy into mechanical energy and vice versa. It is mainly composed of an ionic polymer metal composite (ionic polymer EAP) and a conductive polymer conducting polymer, and electromechanical EAP, dielectric elastomer and electrostrictive polymer. They have different properties and different applications. Among these, ionic polymer metal complexes are considered to be the most suitable materials for application in the display field with a low driving voltage and a relatively fast response speed, but they have difficulties in using them as a matrix of photonic crystals. The preparation of EAP using the redox property of a crosslinked polymer containing an organo-metallic component may be an alternative wherein the monomers comprising the double ferrocene group are resistant to oxygen and moisture , It is possible to perform reversible redox electrochemistry in a variety of solvents, so that it is used as a monomer which is very useful for obtaining EAP of excellent performance.

Such monomers are known to polymerize via ring-opening polymerization (ROP) pathways by thermal polymerization, metal-catalyzed polymerization, and the like. In the case of dual thermal polymerization, the conditions of high temperature and inert atmosphere at 130 to 280 ° C are required and are not effective in controlling the molecular weight of the polymer.

Anionic polymerization is capable of polymerization under relatively relaxed conditions, has a high polymerization rate and is easy to control molecular weight, but it is necessary to use an extremely purity monomer obtained through a multi-step purification process. Polymerization using a platinum compound does not require high-temperature conditions or high-purity monomers, which are main disadvantages of thermal polymerization and anionic polymerization, but it has a difficulty in molecular weight control.

One task is to provide a poly (ferrocenyl) silane-based network polymer that can be prepared by a simple process.

Another object of the present invention is to provide a method for producing the network polymer.

Another object is to provide a film comprising the network polymer.

As one embodiment, there is provided a poly (ferrocenyl) silane network polymer comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (3)

≪ Formula 1 >

(2)

(3)

In the formulas, Fc represents a perovskhenylene group of the following formula (4a), DFc represents a diepselocyaninyl linkage group of the following formula (4b), m1 and m2 each independently represent a number of 0 or 1;

≪ Formula 4a &

Wherein m4 represents a number from 1 to 10;

<Formula 4b>

In the formula,

N ₁ and n ₂ each independently represent a number of from 5 to 95,

또는

을 나타내고, 여기서 R₁ 및 R₂는 각각 독립적으로 치환 또는 비치환된 탄소수 1 내지 20의 알킬기 또는 치환 또는 비치환된 탄소수 1 내지 30의 아릴기를 나타내고, X₂는 -O-, -S-, 탄소수 1 내지 20의 치환 또는 비치환된 알킬렌기, 혹은 탄소수 1 내지 30의 치환 또는 비치환된 아릴렌기를 나타낸다.X &lt; ₁ &gt;

or

, Wherein each of R ₁ and R ₂ independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 1 to 30 carbon atoms, X ₂ is -O-, -S-, A substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 1 to 30 carbon atoms.

According to one embodiment, the poly (ferrocenyl) silane-based network polymer can be obtained by crosslinking a base polymer of the following formula (5) and a crosslinking agent of the following formula (6):

&Lt; Formula 5 >

In the formula,

N ₁ and n ₂ each independently represent a number of from 5 to 95,

M3 represents a number of 0 or 1,

또는

을 나타내고, 여기서 R₁ 및 R₂는 각각 독립적으로 치환 또는 비치환된 탄소수 1 내지 20의 알킬기 또는 치환 또는 비치환된 탄소수 1 내지 30의 아릴기를 나타내고, X₂는 -O-, -S-, 탄소수 1 내지 20의 치환 또는 비치환된 알킬렌기, 혹은 탄소수 1 내지 30의 치환 또는 비치환된 아릴렌기를 나타낸다;X &lt; ₁ &gt;

or

, Wherein each of R ₁ and R ₂ independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 1 to 30 carbon atoms, X ₂ is -O-, -S-, A substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 1 to 30 carbon atoms;

(6)

Wherein n ₃ represents a number of 1 to 10, R ₃ represents hydrogen or a ferrocenyl group represented by the following formula (13)

Hydrogen / (hydrogen + ferrocenyl group) which is present in the case where R ₃ is hydrogen and ferrocenyl group has a value of 0.1 to 0.9:

&Lt; Formula 13 >

In the formulas, m4 represents a number of 1 to 10.

According to one embodiment, the poly (ferrocenyl) silane-based network polymer may form a polymer film having improved electrical characteristics.

According to one aspect of the present invention, it is possible to produce a poly (ferrocenyl) silane network polymer by a simplified process, and the platinum catalyst can be used both for the production of a base polymer and a crosslinking agent, situ reaction, the intermediate product can be carried out without purification, and the reaction can be carried out under relaxed conditions such as heating in the final crosslinking step.

Further, in the production of a crosslinked polymer film using the network polymer, the substrate to be coated with the film is previously treated with a vinyl group to perform functionalization, and then the crosslinking agent is grafted to prevent an excessive amount of poly (ferrocenyl) silane from being used, It is possible to improve the physical properties of the device while minimizing the decrease in the characteristics.

Fig. 1 shows electrical characteristics of the polymer film obtained in Example 1. Fig.

According to one aspect of the present invention, there is provided a poly (ferrocenyl) silane-based network polymer which is a crosslinking polymer as an electroactive material, wherein the network polymer comprises a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (Pericenyl) silane-based network polymer comprising: &lt; RTI ID = 0.0 &gt;

&Lt; Formula 1 >

(2)

(3)

In the formulas, Fc represents a perovskhenylene group of the following formula (4a), DFc represents a diepselocyaninyl linkage group of the following formula (4b), m1 and m2 each independently represent a number of 0 or 1;

&Lt; Formula 4a &

Wherein m4 represents a number from 1 to 10;

<Formula 4b>

In the formula,

N ₁ and n ₂ each independently represent a number of from 5 to 95,

또는

을 나타내고, 여기서 R₁ 및 R₂는 각각 독립적으로 치환 또는 비치환된 탄소수 1 내지 20의 알킬기 또는 치환 또는 비치환된 탄소수 1 내지 30의 아릴기를 나타내고, X₂는 -O-, -S-, 탄소수 1 내지 20의 치환 또는 비치환된 알킬렌기, 혹은 탄소수 1 내지 30의 치환 또는 비치환된 아릴렌기를 나타낸다.X &lt; ₁ &gt;

or

, Wherein each of R ₁ and R ₂ independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 1 to 30 carbon atoms, X ₂ is -O-, -S-, A substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 1 to 30 carbon atoms.

According to one embodiment, the degree of polymerization of the repeating unit of Formula 1 in the network polymer is, for example, about 5 to about 100, and the degree of polymerization of the repeating unit of Formula 2 is, for example, about 5 to about 100, The degree of polymerization of the repeating unit represented by the formula (3) is, for example, from about 10 to about 25.

According to one embodiment, when the repeating unit of Formula 1 is repeated, the repeating unit of Formula 2 and / or the repeating unit of Formula 3 may be interposed therebetween.

A poly (ferrocenyl) silane network polymer comprising repeating units of the following formula (1), repeating units of the following formula (2) and repeating units of the following formula (3) is prepared by polymerizing a base polymer of the following formula Can:

&Lt; Formula 5 >

In the formula,

N ₁ and n ₂ each independently represent a number of from 5 to 95,

M3 represents a number of 0 or 1,

또는

을 나타내고, 여기서 R₁ 및 R₂는 각각 독립적으로 치환 또는 비치환된 탄소수 1 내지 20의 알킬기 또는 치환 또는 비치환된 탄소수 1 내지 30의 아릴기를 나타내고, X₂는 -O-, -S-, 탄소수 1 내지 20의 치환 또는 비치환된 알킬렌기, 혹은 탄소수 1 내지 30의 치환 또는 비치환된 아릴렌기를 나타낸다;X &lt; ₁ &gt;

or

, Wherein each of R ₁ and R ₂ independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 1 to 30 carbon atoms, X ₂ is -O-, -S-, A substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 1 to 30 carbon atoms;

(6)

Wherein n ₃ represents a number of 1 to 10, R ₃ represents hydrogen or a ferrocenyl group represented by the following formula (13)

Hydrogen / (hydrogen + ferrocenyl group) which is present in the case where R ₃ is hydrogen and ferrocenyl group has a value of 0.1 to 0.9:

&Lt; Formula 13 >

In the formulas, m4 represents a number of 1 to 10.

Polymers according to one embodiment may have various repeating units in its main chain, and these repeating units are described separately for convenience, but they may be understood as various structures such as block copolymers or random copolymers.

In the case of m3 = 0 in the base polymer of Formula 5, it can be represented by the following base polymer of Formula 7:

&Lt; Formula 7 >

N ₁ and n ₂ each independently represent a number of from 5 to 95,

또는

을 나타내고, 여기서 R₁ 및 R₂는 각각 독립적으로 치환 또는 비치환된 탄소수 1 내지 20의 알킬기 또는 치환 또는 비치환된 탄소수 1 내지 30의 아릴기를 나타내고, X₂는 -O-, -S-, 탄소수 1 내지 20의 치환 또는 비치환된 알킬렌기, 혹은 탄소수 1 내지 30의 치환 또는 비치환된 아릴렌기를 나타낸다.X &lt; ₁ &gt;

or

, Wherein each of R ₁ and R ₂ independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 1 to 30 carbon atoms, X ₂ is -O-, -S-, A substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 1 to 30 carbon atoms.

 - Preparation of base polymer

The base polymer of formula (7) can be prepared by the following reaction scheme 1:

<Reaction Scheme 1>

In the formula,

또는

을 나타내고, 여기서 R₁ 및 R₂는 각각 독립적으로 치환 또는 비치환된 탄소수 1 내지 20의 알킬기 또는 치환 또는 비치환된 탄소수 1 내지 30의 아릴기를 나타내고, X₂는 -O-, -S-, 탄소수 1 내지 20의 치환 또는 비치환된 알킬렌기, 혹은 탄소수 1 내지 30의 치환 또는 비치환된 아릴렌기를 나타내고,X &lt; ₁ &gt;

or

, Wherein each of R ₁ and R ₂ independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 1 to 30 carbon atoms, X ₂ is -O-, -S-, A substituted or unsubstituted alkylene group having 1 to 20 carbon atoms or a substituted or unsubstituted arylene group having 1 to 30 carbon atoms,

N ₁ and n ₂ each independently represent a number of from 5 to 95,

And n represents n ₁ + n ₂ .

The production process of the above Reaction Scheme 1 is a process for producing a linear base polyphenecenylsilane, which comprises reacting the dihydrosilane compound of Formula 8 with dimethylsila [1] ferro senopane of Formula 9, After preparing a linear oligopiperosilylsilane of the above formula (10) having Si-H at the terminal thereof, an excessive amount of tetravinylsilane is added to obtain an oligoperocenylsilane of the above formula (7) having a trivinylsilyl end by a hydrosilylation reaction . The sum of n ₁ and n ₂ in the base polymer of formula (7) may have a value of from about 10 to about 100.

The ring-opening polymerization reaction and the hydrosilylation reaction in the above reaction scheme 1 can all be carried out under a platinum-based catalyst. Examples of the platinum-based catalyst include Pt [(CH ₂ ═CH-SiMe ₂ ), Carstedt's catalyst, ₂ O] _1.5 , and Pt [(C ₂ H ₄ ) Cl ₂ ] ₂ , which is a Zeise salt dimmer, can be used. Such a catalyst may be used in an amount of 0.01 mol% to 1 mol% based on 1 mol of the reactant.

The above hydrosilylation reaction can increase the reaction rate by 2 to 10 times by using an excessive amount of Si (vinyl) ₄ , and excess Si (vinyl) ₄ remaining in the reaction can be removed under vacuum.

In the process of Scheme 1, benzene, toluene, xylene and the like may be used as the organic solvent. For example, the reaction may be carried out at 10 to 50 ° C for 1 to 48 hours.

When the base polymer of Formula 7 is further reacted with tetravinylsilane and the linear oligopiperosilylsilane of Formula 10 in the presence of a platinum catalyst, the base polymer of Formula 11, that is, the base polymer of Formula 5, m3 = 1 can be obtained.

&Lt; Formula 11 >

In the formula,

또는

을 나타내고, 여기서 R₁ 및 R₂는 각각 독립적으로 치환 또는 비치환된 탄소수 1 내지 20의 알킬기 또는 치환 또는 비치환된 탄소수 1 내지 30의 아릴기를 나타내고, X₂는 -O-, -S-, 탄소수 1 내지 20의 치환 또는 비치환된 알킬렌기, 혹은 탄소수 1 내지 30의 치환 또는 비치환된 아릴렌기를 나타내고,X &lt; ₁ &gt;

or

, Wherein each of R ₁ and R ₂ independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 1 to 30 carbon atoms, X ₂ is -O-, -S-, A substituted or unsubstituted alkylene group having 1 to 20 carbon atoms or a substituted or unsubstituted arylene group having 1 to 30 carbon atoms,

N ₁ and n ₂ each independently represent a number of from 5 to 95;

- Preparation of crosslinking agent

The compound of Formula 6, which is a crosslinking agent that reacts with the base polymer of Formula 5, can be prepared by the following Reaction Scheme 2:

<Reaction Scheme 2>

Wherein, R ₄ is present with the case of methyl or hydrogen, R ₃ is present with the case ferrocenyl group of the methyl group or the formula 13 and, n ₃ is a number of 10 to 25:

&Lt; Formula 13 >

In the formulas, m4 represents a number of 1 to 10.

The reaction scheme 2 is a process for producing the crosslinking agent of Formula 6, wherein the poly (dimethylsiloxane) represented by Formula 12 and the dimethylsilyl [1] perrosene represented by Formula 9 are reacted in the presence of a platinum- A crosslinking agent of formula (7) can be obtained.

The poly (dimethylsiloxane) of the formula (12) as a starting material is subjected to a process in which a part of the methyl groups are substituted with hydrogen, and the substituted hydrogen is replaced with the ferrocenyl group of the above formula (13). That is, the substituent R ₄ in the poly (dimethylsiloxane) of Chemical Formula 12 may be a methyl or hydrogen atom, and the hydrogen substitution ratio of the methyl group, that is, H / (H + methyl) In the range of about 0.1 to 0.5, and when the substitution ratio is 0.5, it means that hydrogen and methyl groups are present in a ratio of 1: 1 as R ₄ .

Hydrogen and a methyl group coexist as R ₄ , and the hydrogen located at R ₄ can be substituted with the ferrocenyl group of the above formula (13) through the process of the above-mentioned Reaction Scheme 2. That is, the substituent of R ₃ present in the crosslinking agent of the formula (6) are to co-exist group ferrocenyl of hydrogen and the formula (13), the ratio of the ferrocenyl group at this time is a value similar to the substitution ratio of hydrogen present in the R ₄ Lt; / RTI &gt; That is, when the hydrogen and the methyl groups are present in a ratio of 1: 1 as R ₄ , the ratio of the presence of the methyl group and the ferrocenyl group in the R ₃ can be about 1: 1.

In the above Reaction Scheme 2, a reaction scheme in the case where hydrogen and methyl groups are present in a ratio of 1: 1 as R ₄ is shown as the following Reaction Scheme 3:

<Reaction Scheme 3>

Wherein R ₄ is a methyl group or a hydrogen, and they are present in a ratio of 1: 1, n ₃ is a number of 10 to 25, and m ₄ is a number of 1 to 10, respectively.

In the above Reaction Scheme 3, R ₄ is a methyl group or hydrogen, and when they are present in a ratio of 1: 1, the dimethylsilyl [1] ferro senopane of Formula 9 is substituted with the hydrogen, And ferrocenyl groups are present in a ratio of 1: 1.

The process of Scheme 2 may be performed using benzene, toluene, xylene or the like as an organic solvent, and may be carried out at 10 to 50 ° C for 1 to 48 hours.

Examples of the platinum-based catalyst include Pt [(CH ₂ = CH-SiMe ₂ ) ₂ O] _1.5 , a Carstedt's catalyst, Pt [(C ₂ H ₄ ) Cl ₂ ] ₂ which is a dimer (Zeise salt dimmer) can be used. Such a catalyst may be used in an amount of 0.01 mol% to 1 mol% based on 1 mol of the reactant.

- Preparation of poly (ferrocenyl) silane network polymer

After preparing the base polymer and the cross-linking agent as described above, they can be reacted in the presence of platinum as shown in the following Reaction Scheme 4 to prepare a poly (ferrocenyl) silane-based network polymer.

<Reaction Scheme 4>

In the formula,

또는

을 나타내고, 여기서 R₁ 및 R₂는 각각 독립적으로 치환 또는 비치환된 탄소수 1 내지 20의 알킬기 또는 치환 또는 비치환된 탄소수 1 내지 30의 아릴기를 나타내고, X₂는 -O-, -S-, 탄소수 1 내지 20의 치환 또는 비치환된 알킬렌기, 혹은 탄소수 1 내지 30의 치환 또는 비치환된 아릴렌기를 나타내고,X &lt; ₁ &gt;

or

, Wherein each of R ₁ and R ₂ independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 1 to 30 carbon atoms, X ₂ is -O-, -S-, A substituted or unsubstituted alkylene group having 1 to 20 carbon atoms or a substituted or unsubstituted arylene group having 1 to 30 carbon atoms,

N ₁ and n ₂ each independently represent a number of from 5 to 95,

M3 represents a number of 0 or 1,

R ₃ is a methyl group or a perovskenyl group of the following formula (13), and n ₃ is a number of 10 to 25:

&Lt; Formula 13 >

In the formulas, m4 represents a number of 1 to 10.

In the process of Reaction Scheme 4, one of the vinyl groups present at one end of the base polymer of Formula 5 is cross-linked with the terminal hydrogen of the perovskyl group present in the cross-linking agent of Formula 6. That is, the Si and the R ₃ is a methyl group in the crosslinking agent of the formula (6) does the base polymer of the general formula (5) is not cross-linked, in the cross-linking agent of Formula (VI) R ₃ is cross-linked only when ferrocenyl group is coupled to the base polymer .

As a result of such a crosslinking reaction, the resulting poly (ferrocenyl) silane network polymer will comprise a repeating unit of the following formula (1), a repeating unit of the following formula (2) and a repeating unit of the following formula (3)

&Lt; Formula 1 >

(2)

(3)

In the formulas, Fc represents a perovskhenylene group of the following formula (4a), DFc represents a diepselocyaninyl linkage group of the following formula (4b), m1 and m2 each independently represent a number of 0 or 1;

&Lt; Formula 4a &

Wherein m4 represents a number from 1 to 10;

<Formula 4b>

In the formula,

N ₁ and n ₂ each independently represent a number of from 5 to 95,

또는

을 나타내고, 여기서 R₁ 및 R₂는 각각 독립적으로 치환 또는 비치환된 탄소수 1 내지 20의 알킬기 또는 치환 또는 비치환된 탄소수 1 내지 30의 아릴기를 나타내고, X₂는 -O-, -S-, 탄소수 1 내지 20의 치환 또는 비치환된 알킬렌기, 혹은 탄소수 1 내지 30의 치환 또는 비치환된 아릴렌기를 나타낸다.X &lt; ₁ &gt;

or

, Wherein each of R ₁ and R ₂ independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 1 to 30 carbon atoms, X ₂ is -O-, -S-, A substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 1 to 30 carbon atoms.

The repeating unit represented by the formula (1) means that the vinyl group present at both ends of the base polymer of the formula (5) is crosslinked with the crosslinking agent of the formula (6). The repeating unit of the formula (2) Refers to a case where only the vinyl group present in the polymer is crosslinked with the crosslinking agent of the above formula (6), and the repeating unit of the above formula (3) refers to the crosslinking agent not crosslinked with the base polymer.

In the process of Scheme 4, benzene, toluene, xylene and the like may be used as the organic solvent, and the reaction may be carried out at 30 to 80 ° C for 1 to 48 hours.

Examples of the platinum-based catalyst include Pt [(CH ₂ = CH-SiMe ₂ ) ₂ O] _1.5 , a Carstedt's catalyst, Pt [(C ₂ H ₄ ) Cl ₂ ] ₂ which is a dimer (Zeise salt dimmer) can be used. Such a catalyst may be used in an amount of 0.01 mol% to 1 mol% based on 1 mol of the reactant.

The network structure of the poly (ferrocenyl) silane network polymer according to one embodiment has a network structure in which all of the repeating units of the above formulas (1), (2) and (3) are mixed, and the network structure is not a linear structure, Can be structured to be two-dimensionally coupled to each other.

For example, the repeating units of the above formula (1) may have a structure in which repeating units of the above-mentioned formulas (2) and (3) are interposed in the middle of the ladder-

Specific examples of the poly (ferrocenyl) silane network polymer in which the repeating units represented by the above formulas (1), (2) and (3) are all mixed include the following formula (15)

&Lt; Formula 15 >

를 나타내며, Fc 및 DFc는 상기 정의한 바와 같다.In the formula, A is

, And Fc and DFc are as defined above.

As shown in Formula 15, the network polymer may have a two-dimensional structure instead of a simple linear structure, and it may be known that the base polymer of Formula 5 is linked to the crosslinking agent of Formula 6 by monodentate or bidentate method. .

In the structural formula (15), the repeating units 1, 2 and 3 may be represented by the following general formula (16)

&Lt; Formula 16 >

를 나타내며, Fc 및 DFc는 상기 정의한 바와 같다.In the formula, A is

, And Fc and DFc are as defined above.

In the structural formula (16), a represents an example of a repeating unit of the formula (1), b represents an example of a repeating unit of the formula (2), and c represents an example of a repeating unit of the formula (3).

- Formation of poly (ferrocenyl) silane based polymer film

The poly (ferrocenyl) silane-based polymer having a network structure as described above may be formed into a film using various substrates such as glass, ITO, plastic, spin coating, dip coating, solvent casting or the like It is possible.

The poly (ferrocenyl) silane network polymer as described above can use one kind of sila [1] ferro senopane as a starting material without the need to synthesize various kinds of sila [1] ferro senopane, It is not sensitive to the purity, and the desired purity can be obtained by only the recrystallization step of three to four steps. In addition, it is preferable that the base polymer has a main chain length and an amount of vinylsilic moiety cross-linked, depending on the ratio of sila [1] ferrosenopan, dihydro silane and tetravinyl silane used as raw materials. In addition, the crosslinking agent is easily saturated with the ferrocene moiety, making it possible to increase the electrochemically active species in the poly (ferrocenyl) silane network polymer.

In addition, both of the base polymer and the crosslinking agent can be produced in situ without requiring a separate step of separating each component. 0.02 to 0.5 mol% of the platinum-based catalyst relative to the Si-H unit is used in all the steps in the same manner and remains active, so that it is not necessary to repeat the addition when added at the starting point.

In addition, ultraviolet irradiation and an inert atmosphere are not necessary in the curing process for obtaining the resultant product, and the reaction can be terminated only at about 50 to 70 ° C for several hours.

The base polymer and the cross-linking agent for forming the network polymer can be used immediately when needed, so that they can be preserved without deterioration even if they are prepared and stored in advance.

 Therefore, the poly (ferrocenyl) silane network polymer can be produced and mass-produced by a simple process, can be used as an active ingredient of the controllable photonic crystal, and can be used as a transparent actuator, a biosensor, a counter redox material ) Can be used.

 On the other hand, when the poly (ferrocenyl) silane network polymer is used as a photonic crystal display device, the content of the ferrocene moiety, which is an electroactive redox component, can be maximized, , It is possible to maximize the cross-linking density, so that it can be used for development of a display device close to the demand of consumers, such as an improvement in the switching speed, an increase in the color realization range, and an increase in the durability.

Hereinafter, embodiments of the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

[Example 1]

a) Preparation of crosslinking agent

Hydrogenated polydimethylsiloxane Me [(HSiMeO) (SiMe ₂ O)] ₆ SiMe ₃ (65 mg, 0.4 mmol, Si-H) and a zeic salt dimer [Pt (C ₂ H ₄ ) Cl ₂ ] ₂ (10 mM, 0.8 mL, 1 mol%) was added to a solution of FcSiMe ₂ (200 mg, 0.8 mmol) dissolved in 1.2 mL of benzene and mixed for 3 to 5 hours. The molecular weight of the obtained cross-linking agent, Me [(RSiMeO) (SiMe ₂ O)] ₆ SiMe ₃ (R = - (FcSiMe ₂ ) ₂ H) is approximately 3,800 and the content of ferrocene moieties is approximately 75% Group / (methyl group + perocenyl group) X100).

b) Preparation of Base Polymer: Tribinylsilyl capped polyferrocenylsilane &lt; RTI ID = 0.0 &gt;

Carstedt's catalyst (Aldrich) was added to 0.24 g (1.00 mmol) dimethylsila [1] ferrocenophane in 19 ml (0.10 mmol) of diphenylsilane Ph ₂ SiH ₂ dissolved in 3 ml benzene at 25 ° C, , 2% Pt in xylene, 5,, 0.43 mol% to Ph ₂ SiH ₂ ) were added with stirring and the reaction was completed for 1-3 hours. The reaction was confirmed by NMR.

_{1H NMR (δ, CDCl 3)} : 7.57-7.64 (oH, Ph, 4H); 7.35-7.41 (mH and pH, Ph, 6H); 3.9-4.3 (C5H4, Fc, 77H), 0.25-0.55 (SiMe2, 58H); 5.44 (Ph2Si-H, 0.2-0.7H); 4.42 (Me2Si-H, 1.3-1.8H).

To the solution prepared above, tetravinylsilane (340 ul, 2 mmol, 10 times excess) was added and the reaction was carried out for 3 days. After removing the solvent, the residue was dried.

_{1H NMR (δ, CDCl 3)} : 7.50-7.62 (oH, Ph, 4H); 7.32-7.40 (mH and pH, 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 crosslinked polyhydroferrocenylsilane

(Me ₃ Si - [(OSiMeH) (OSiMe ₂ ) ₆ ] ₃ ] ₃ (0.07 mmol) dissolved in 3 ml benzene was added dropwise to a solution of 0.26 g (1.1 mmol) of dimethylsilaferrocenophane and 0.087 g (0.09 mmol) of polyhydrosiloxane Carstedt's catalyst (Aldrich, 2% Pt in xylene, 3 ul, 0.26 umol Pt, 0.25 mol% to Si-H) was added to the solution with stirring. After 3 hours of reaction, the solvent was removed and dried.

_{^{1 H 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) Production of PFS film

The reactants prepared in b) and c) are mixed and left at room temperature for 1 day. The coating is applied to a glass base material by a spin coating method and then treated at 70 ° C for 3-12 hours to obtain a transparent yellowish-orange glassy coating.

 Experimental Example

The film obtained in Example 1 was subjected to electrical characteristics by a cyclic voltammetry method and is shown in FIG. As shown in FIG. 1, it can be seen that the redox process proceeds reversibly.

Claims (12)

A poly (ferrocenyl) silane network polymer comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (3)
&Lt; Formula 1 >

(2)

(3)

In the formulas, Fc represents a perovskhenylene group of the following formula (4a), DFc represents a diepselocyaninyl linkage group of the following formula (4b), m1 and m2 each independently represent a number of 0 or 1;
&Lt; Formula 4a &

Wherein m4 represents a number from 1 to 10;
<Formula 4b>

In the formula,
N ₁ and n ₂ each independently represent a number of from 5 to 95,
X < ₁ >

or

, Wherein each of R ₁ and R ₂ independently represents an unsubstituted alkyl group having 1 to 20 carbon atoms or an unsubstituted aryl group having 6 to 30 carbon atoms, X ₂ is -O-, -S-, , Or an unsubstituted arylene group having 6 to 30 carbon atoms. The method according to claim 1,
Wherein the polymerization degree of the repeating unit represented by Formula 1 is 5 to 100, the degree of polymerization of the repeating unit represented by Formula 2 is 5 to 100, and the degree of polymerization of the repeating unit represented by Formula 3 is 10 to 25, Network polymer. The method according to claim 1,
Wherein the repeating unit of the formula (2) and / or the repeating unit of the formula (3) are interposed between the repeating units of the formula (1). A method for producing a poly (ferrocenyl) silane network polymer comprising: crosslinking a base polymer represented by the following formula (5) and a crosslinking agent represented by the following formula (6)
&Lt; Formula 5 >

In the formula,
N ₁ and n ₂ each independently represent a number of from 5 to 95,
M3 represents a number of 0 or 1,
X < ₁ >

or

, Wherein each of R ₁ and R ₂ independently represents an unsubstituted alkyl group having 1 to 20 carbon atoms or an unsubstituted aryl group having 6 to 30 carbon atoms, X ₂ is -O-, -S-, An unsubstituted alkylene group or an unsubstituted arylene group having 6 to 30 carbon atoms;
(6)

Wherein n ₃ represents a number of 10 to 25, R ₃ represents a methyl group or a perovskenyl group of the following formula (13)
The ferrocenyl group / (methyl group + ferrocenyl group), which is present in the case where R ₃ is methyl group and ferrocenyl group, has a value of 0.1 to 0.9:
&Lt; Formula 13 >

In the formulas, m4 represents a number of 1 to 10. 5. The method of claim 4,
Wherein the base polymer of formula (5) is a base polymer of formula (7): < EMI ID =
&Lt; Formula 7 &gt;

N ₁ and n ₂ each independently represent a number of from 5 to 95,
X &lt; ₁ &gt;

or

, Wherein each of R ₁ and R ₂ independently represents an unsubstituted alkyl group having 1 to 20 carbon atoms or an unsubstituted aryl group having 6 to 30 carbon atoms, X ₂ is -O-, -S-, , Or an unsubstituted arylene group having 6 to 30 carbon atoms. 6. The method of claim 5,
The base polymer of Formula 7 is reacted with dihydrosilane of Formula 8 and dimethylsilyl [1] ferrosenopyran of Formula 9 in the presence of a platinum-based catalyst to obtain a linear oligomer of Formula 10 having Si- (Ferrocenyl) silane-based network polymer obtained by reacting perovskyl silane in the presence of tetravinyl silane,

In the formula,
X &lt; ₁ &gt;

or

, Wherein each of R ₁ and R ₂ independently represents an unsubstituted alkyl group having 1 to 20 carbon atoms or an unsubstituted aryl group having 6 to 30 carbon atoms, X ₂ is -O-, -S-, An unsubstituted alkylene group or an unsubstituted arylene group having 6 to 30 carbon atoms,
N ₁ and n ₂ each independently represent a number of from 5 to 95,
And n represents n ₁ + n ₂ . The method according to claim 6,
The base polymer of Formula 7 is further reacted with tetravinylsilane and the linear oligopiperosilylsilane of Formula 10 in the presence of a platinum catalyst to prepare a base polymer of Formula 11 (Ferrocenyl) silane-based network polymer comprising the steps of:
&Lt; Formula 11 >

In the formula,
X &lt; ₁ &gt;

or

, Wherein each of R ₁ and R ₂ independently represents an unsubstituted alkyl group having 1 to 20 carbon atoms or an unsubstituted aryl group having 6 to 30 carbon atoms, X ₂ is -O-, -S-, An unsubstituted alkylene group or an unsubstituted arylene group having 6 to 30 carbon atoms,
N ₁ and n ₂ each independently represent a number of from 5 to 95; 5. The method of claim 4,
Wherein the crosslinking agent of the formula (6) is obtained by reacting a poly (dimethylsiloxane) represented by the following formula (12) and a dimethylsilyl [1] Method of producing network polymer:

Wherein, R ₄ is present with the case of methyl or hydrogen, R ₃ is present with the case ferrocenyl group of the methyl group or the formula 13 and, n ₃ is a number of 10 to 25:
&Lt; Formula 13 >

In the formulas, m4 represents a number of 1 to 10. 9. The method of claim 8,
Wherein the substituent R ₄ in the poly (dimethylsiloxane) of Chemical Formula 12 is a methyl or hydrogen atom, and the ratio of H / (H + methyl), which is the hydrogen substitution ratio of the methyl group, is in the range of 0.1 to 0.9. Method of making network polymer. 9. The method of claim 8,
Wherein the substituent R ₃ in the above formula (6) is methyl and the ferrocenyl group of the above-mentioned formula (13), and the ratio thereof is in the range of 0.1 to 0.9 in terms of the ferrocenyl group / (methyl group + ferrocenyl group) Chenylene) silane network polymer. 5. The method of claim 4,
Wherein the poly (ferrocenyl) silane network polymer comprises a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (3)
&Lt; Formula 1 >

(2)

(3)

In the formulas, Fc represents a perovskhenylene group of the following formula (4a), DFc represents a diepselocyaninyl linkage group of the following formula (4b), m1 and m2 each independently represent a number of 0 or 1;
&Lt; Formula 4a &

Wherein m4 represents a number from 1 to 10;
<Formula 4b>

In the formula,
N ₁ and n ₂ each independently represent a number of from 5 to 95,
X < ₁ >

or

, Wherein each of R ₁ and R ₂ independently represents an unsubstituted alkyl group having 1 to 20 carbon atoms or an unsubstituted aryl group having 6 to 30 carbon atoms, X ₂ is -O-, -S-, , Or an unsubstituted arylene group having 6 to 30 carbon atoms. A polymer film comprising the substrate and the poly (ferrocenyl) silane network polymer according to any one of claims 1 to 3 bonded to the substrate.

Images