KR101195534B1 - Process for Preparation of Polythiophene Star Polymer and Polythiophene Star Polymer Prepared By the Same - Google Patents

Abstract

(상기 식에서, n은 0 내지 12, m은 1 내지 90)
상기 폴리(3-알킬티오펜) 매크로 개시제에 1종 이상의 디비닐 단량체 또는 1종 이상의 디비닐 단량체와 1종 이상의 비닐 단량체를 첨가하여 폴리티오펜 스타 폴리머를 중합하는 단계를 포함하는 폴리티오펜 스타 폴리머의 제조방법 및 이로부터 제조된 폴리티오펜 스타 폴리머에 관한 것이다. 본 발명의 따르면, 가용성이 우수한 고분자량의 폴리티오펜 스타 폴리머를 제공할 수 있다.The present invention comprises the steps of forming a polythiophene macro initiator having a functional group capable of living radical polymerization at the polythiophene terminal of the formula: And

Wherein n is 0 to 12 and m is 1 to 90
A polythiophene star comprising polymerizing a polythiophene star polymer by adding at least one divinyl monomer or at least one divinyl monomer and at least one vinyl monomer to the poly (3-alkylthiophene) macro initiator. It relates to a process for producing a polymer and a polythiophene star polymer prepared therefrom. According to the present invention, it is possible to provide a high molecular weight polythiophene star polymer having excellent solubility.

Description

Process for Preparation of Polythiophene Star Polymer and Polythiophene Star Polymer Prepared By the Same

The present invention relates to a method for producing a polythiophene star polymer and a polythiophene star polymer prepared by using the same, and more particularly, to a polyti having a high molecular weight three-dimensional structure by controlling the structure of the regioregular polythiophene. The present invention relates to a process for preparing an open star polymer and a polythiophene star polymer produced thereby.

Polythiophene is a material that can be used in organic solar cells, smart window systems, optoelectronics and organic light emitting diodes (OLED), liquid crystal display (LCD).

Polythiophene conductive polymer synthesis is generally synthesized through metal-catalyzed cross-reactions, but Grignard Metathesis found by McCullough (Richard D. McCullough, macromolecules 2005, 38, 10346-10352) and others. : GRIM) method exhibits Regioregularity, in which the side chain of polythiophene is almost composed of head-to-tail (HT), which has significantly improved electron and photon properties compared to existing positional random analogs.

Synthesis of polythiophene conductive polymers by GRIM method is known to control the molecular weight and molecular weight distribution as well as the properties of regioregularity. Such quasi living polymerization of thiophene is based on McClow and Yoko Yokozawa [Tsutomu Yokozawa, J. AM. CHEM. SOC., 2005, 127, 17542-17547.

Living polymerization method has little side reactions such as stop reaction that can occur during polymerization, so the molecular weight can be predicted by the amount of monomer and initiator used. In general, the obtained polymer has a narrow molecular weight distribution and the terminal is alive. When added again, the molecular weight is characterized by a continuous increase. Using this, block copolymers and the like can be synthesized. In the GRIM method, the Ni (II) catalyst acts as an initiator to control the molecular weight. The living polymerization method is classified into a living radical polymerization method, a living anion heavy rice method, and a living cation polymerization method according to the kind of initiator used.

A star polymer generally refers to a polymer having a three-dimensional structure in which a plurality of linear polymers are chemically linked to a central point. Star polymers have very low viscosity due to their compact structure and low hydrodynamic volume, compared to linear polymers having the same molecular weight, and have very high solubility.

According to the research results of the present inventors, since a conductive polymer such as polythiophene is generally a structure in which an aromatic compound or an olefin compound of a resonance structure is repeatedly connected to the main chain, solubility in an organic solvent is poor, resulting in a high molecular weight polymer. There are many difficulties in the synthesis, and in order to overcome this problem, the availability of the alkane group, which is an soluble group, is increased in the side chain to increase the solubility. There are disadvantages.

In addition, research on synthesis and physical properties of polythiophene has been conducted mainly on a linear two-dimensional structure, and research on synthesis and physical properties of polythiophene having a three-dimensional structure such as star polymers is very poor. .

It is an object of the present invention to provide a polythiophene star polymer having a high molecular weight three-dimensional structure with excellent solubility without reducing the conductivity of the polythiophene. To this end, the inventors have found that when forming a polythiophene macro initiator having a functional group capable of living radical polymerization at the polythiophene end, it is used as a precursor of living radical polymerization. This has led to the production of high molecular weight novel polythiophene star polymers having arms and characteristic cores containing polythiophenes.

According to one embodiment of the present invention, forming a polythiophene macro initiator having a functional group capable of living radical polymerization at the polythiophene terminal of the formula: And

Wherein n is 0 to 12 and m is 1 to 90

A polythiophene star comprising polymerizing a polythiophene star polymer by adding at least one divinyl monomer or at least one divinyl monomer and at least one vinyl monomer to the poly (3-alkylthiophene) macro initiator. A method for producing a polymer is provided.

According to another embodiment of the present invention, a core comprising at least one selected from the group consisting of homopolymers of block copolymer divinyl monomers, copolymers of divinyl monomers and copolymers of divinyl monomers and vinyl monomers; And

There is provided a polythiophene star polymer having an arm structure comprising a polythiophene of the following formula bonded to the core.

Wherein n is 0 to 12 and m is 1 to 90

According to this invention, the high molecular weight polythiophene star polymer which has a three-dimensional structure can be manufactured easily. In addition, the polythiophene star polymer provided by the present invention is excellent in solubility and can prevent the inherent conductivity from being lowered. Moreover, due to the three-dimensional structure unique to the star polymer, it can be expected to play a role as a functional polymer exhibiting various functionalities that conventional two-dimensional linear polymers are difficult to exhibit.

1 is a ¹ H NMR spectrum of a poly (3-alkylthiophene) macro initiator prepared in an embodiment of the present invention.
2 is a graph showing the conversion rate of the crosslinking agent according to the reaction time in the polymerization process of the polythiophene star polymer according to the embodiment of the present invention.
Figure 3 is a spectrum showing the THF-GPC of the reaction solution measured according to the reaction time in the polymerization process of the polythiophene star polymer according to an embodiment of the present invention.
Figure 4 is a measurement of the polythiophene star polymer separated from the reaction solution and the reaction solution after the completion of the reaction (when the reaction time is 20 hours) in the polymerization process of the polythiophene star polymer according to an embodiment of the present invention, respectively It is the spectrum which shows THF-GPC.
5 is a ¹ H NMR spectrum of a polythiophene star polymer polymerized according to an embodiment of the present invention.

The method for producing a polythiophene star polymer according to the present invention is a polymerization reaction of a polythiophene star polymer according to the amount of polythiophene and at least one divinyl monomer or at least one divinyl monomer and at least one vinyl monomer. Yield and type can be controlled, and polythiophene star polymers having cores of various sizes can be prepared.

The method for producing a polythiophene star polymer according to the present invention includes forming a polythiophene macro initiator having a functional group capable of living radical polymerization at a polythiophene end.

The polythiophene includes both the case where n is 0 in the formula and includes an alkyl group when n is 1 to 12, and when n is not 0, an alkyl group is substituted at the 3-position of the polythiophene. With poly (3-alkylthiophene), the solubility of the poly (3-alkylthiophene) can be adjusted according to the carbon number of the alkyl group.

The polythiophene macro initiator refers to a polythiophene compound having a structure in which a functional group capable of causing an initiation reaction in a polymerization reaction of a polythiophene star polymer is introduced.

In one embodiment, forming the polythiophene macro initiator comprises: forming an allyl group or a vinyl group at the polythiophene end; Introducing a hydroxyl group to the terminal of the polythiophene in which the allyl group or the vinyl group is formed; And the hydroxy group halide compound, benzyl 3-chloro-3-oxopropyl carbonotrithioate, 2-bromo-2-methylpropanoyl bromide and 2 , 2, 5-trimethyl-4-phenyl-3-azahexane-3oxy (TINPO) may include the step of substituting one or more selected from the group consisting of.

The allyl group or vinyl group formed at the terminal of the polythiophene may be formed by, for example, Grignard Metathesis (GRIM) method. According to the GRIM method, various nonpolar groups, such as an allyl group, an alkane group, an alkyne group, and a benzene group, can be introduced at the end of the chain depending on the kind of Grignard reagent used.

Thereafter, a hydroxyl group is introduced into the terminal of the polythiophene in which the allyl group or the vinyl group is formed, and the hydroxyl group is a halide compound, benzyl 3-chloro-3-oxopropyl carbonotrithioate (benzyl 3-). chloro-3-oxopropyl carbonotrithioate), 2-bromo-2-methylpropanoyl bromide and at least one selected from the group consisting of 2, 2, 5-trimethyl-4-phenyl-3-azahexane-3oxy (TINPO) It is possible to convert to a living polymer radical initiator capable of atomic transfer radical polymerization, that is, a polythiophene macro initiator having a functional group capable of living radical polymerization at the terminal of the polythiophene, including the step of substituting the substituent.

In one embodiment, when the hydroxyl group is replaced with a halide compound, a polythiophene macro initiator capable of Atom Transfer Radical Polymerization (ATRP) polymerization in living radical polymerization may be formed. At this time, the halogen element of the halide compound may be the starting point of the atom transfer radical polymerization.

The halide compound is not particularly limited as long as it is a functional group capable of living radical polymerization, for example, 4-methylbenzyl bromide, 4-cyanobenzyl bromide, 4-bromobenzyl bromide, 2-bromopropionitrile, bromoaceto Nitrile, glycidol 2-bromopropionate, tert-butyl 2-bromopropionate, hydroxyethyl 2-bromopropionate, vinyl chloroacetate, allyl chloroacetate, α-bromo-γ- At least one compound selected from the group consisting of butyrolactone, 2-chloroacetamide and ethyl-2-chloro-2-phenyl acetate (ECPA).

The polythiophene star polymer may be ATRP polymerized by thermally activating a polythiophene macroinitiator including a halide compound under a catalyst, and the combination of carbon and a halogen element of the halide compound forms a complex by the catalyst. While forming a radical.

The catalyst may be, for example, a transition metal catalyst of CuX (X = Cl, Br). When using CuX (X = Cl, Br) as a catalyst, it is not necessary to add a separate compound according to the stability of the catalyst, 2,2'-bipyruidine in the step of polymerizing a polythiophene star polymer And one or more ligands selected from derivatives thereof, 2-iminopyruidine and aliphatic polyamine can be further added, and the reaction rate can vary depending on the combination of catalyst and ligand.

The transition metal catalyst is one selected from the group consisting of RuCl ₂ (PPh ₃ ) ₃ , RuH ₂ (PPh ₃ ) ₃ , FeCl ₂ (PPh ₃ ) ₃ , NiBr ₂ (PPh ₃ ) ₃ and Ni (NCN) Br. It may be more than, but is not limited thereto.

Among these, when RuCl ₂ (PPh ₃ ) ₃ is used as the transition metal catalyst, the polythiophene star polymer may be polymerized by further including at least one additive selected from the group consisting of tributylamine and dibutylamine. have. The additive may improve stability and reactivity of the polythiophene star polymer polymerization.

In another embodiment, when the hydroxyl group is substituted with 2, 2, 5-trimethyl-4-phenyl-3-azahexane-3-oxy and / or 2-bromo-2-methylpropanoyl bromide, living Among the radical polymerization methods, polythiophene macro initiators capable of performing NMP (nitroxide-mediated polymerization) polymerization may be formed, and NMP polymerization is a polymerization method in which nitrogen and oxygen bonds are easily formed as radicals, and thus stable polymerization is possible. .

When the hydroxyl group is substituted with benzyl 3-chloro-3-oxopropyl carbonotrithioate, reversible addition-fragmentation chain transfer (RAFT) may be polymerized in living radical polymerization. Polythiophene macroinitiators can be formed, and RAFT polymerization is a method of producing and polymerizing growth radicals in such a way that their ends are reversibly moved under radical attack.

Thereafter, the polythiophene macroinitiator may be polymerized by reacting at least one divinyl monomer or at least one divinyl monomer with at least one vinyl monomer.

The divinyl monomer serves as a crosslinking agent for forming the core of the crosslinking structure, and is not particularly limited as long as it is a crosslinking agent suitable for forming the above structure (hereinafter, the divinyl monomer may also be used as a crosslinking agent in the specification). The divinyl monomer may be, for example, a diacrylate compound, a dimethacrylate compound such as ethylene glycol dimethacrylate, a diacrylamide compound, a divinylphenyl compound, a divinyl naphthalene compound, And it may be at least one selected from the group consisting of divinyl toluene-based compound.

In addition, the vinyl monomers added together with the divinyl monomers are styrene-based, butadiene-based, isoprene-based, methacryl-based, acryl-based, acrylamide-based, methacrylamide-based, acrylonitrile, vinyl acetate, vinylpyridine and vinylpy. It may be one or more selected from the group consisting of rolidone.

In one embodiment, the polythiophene star polymer may be prepared by living radical polymerization of a polythiophene macro initiator and a divinyl monomer or a divinyl monomer and a vinyl monomer, and any living radical polymerization may be applied. For example, the polythiophene star polymer may be prepared by polymerization by nitroxide-mediated polymerization (NMP) polymerization, reversible addition-fragmentation chain transfer (RAFT) polymerization, or atom transfer radical polymerization (ATRP) polymerization.

In another embodiment, the polythiophene star polymer may be prepared by further polymerizing the polythiophene macro initiator with at least one vinyl monomer.

At this time, the polythiophene star polymer is a living radical polymerization, such as nitroxide-mediated polymerization (NMP) polymerization, reversible addition-fragmentation chain transfer (RAFT) polymerization or ATRP (Atom Transfer Radical Polymerization) The step of polymerizing to prepare a polythiophene bonded to a homopolymer or a block copolymer of one or more vinyl monomers, and then a polythiophene bound to the homopolymer or block copolymer of the vinyl monomer And further polymerizing the divinyl monomer or the divinyl monomer and the vinyl monomer.

Hereinafter, a method for preparing a polythiophene star polymer according to the present invention will be described in detail, but the following description is only a specific example and the present invention is not limited thereto.

Preparation of poly (3-alkylthiophene) macro initiators capable of atom transfer radical polymerization

Preparation of poly (3-alkylthiophene) having an allyl group or vinyl group at the terminal

The process of forming the poly (3-alkylthiophene) which has an allyl group or a vinyl group at the terminal using GRIM method is demonstrated.

(1) Synthesis of 2,5-dibromo-3-alkylthiophene monomer

[Reaction Scheme 1]

Referring to Scheme 1, an alkylene brominated magnesium bromide, which is a Grignard reagent, is used as a monomer of 3-bromothiophene under a [1,3-bis (diphenylphosphine) propane] dichloronickel (II) (Ni (dppp) Cl2) catalyst. Alkyl-MgBr) is added to synthesize 3-alkylthiophenes, and then N-bromosuccimide (NBS) is added to synthesize 2,5-dibromo-3-alkylthiophene monomers. At this time, the length of the alkyl group can be adjusted according to the kind of Grignard reagent added to the 3-bromothiophene monomer.

(2) Preparation of poly3-alkylthiophene having an allyl group or vinyl group at the terminal

Scheme 2

The synthesized 2,5-dibromo-3-alkylthiophene monomer is dissolved in dehydrated and degassed tetrahydrofuran (THF), and then reacted with t-butyl-MgCl dissolved in dimethyl ether at room temperature under argon atmosphere. . Subsequently, Ni (dppp) Cl 2, which is a kind of catalyst and initiator, is added to react at room temperature to polymerize the poly3-alkylthiophene. At this time, the molecular weight can be controlled according to the amount of Ni (dppp) Cl 2 is added.

The reaction is carried out by adding a Grignard reagent (Allyl-MgBr or Vinyl-MgBr) having an allyl group or vinyl group to be substituted at the terminal of the polymerized poly3-alkylthiophene, followed by methanol to quench the polymerization. . The synthesized poly3-alkylthiophene was precipitated in methanol, extracted using a glass filter, and purified by a solvent extraction method using pentane to remove a low molecular weight polymer. A poly3-alkylthiophene having an allyl group or a vinyl group introduced therein is prepared.

Preparation of poly (3-alkylthiophene) macro initiators capable of atom transfer radical polymerization

(1) Preparation of poly (3-alkylthiophene) having a hydroxyl group introduced at the terminal

Scheme 3

As shown in Scheme 3, poly (3-alkylthiophene) having an allyl group or vinyl group at the terminal is added to dehydrated and degassed THF, and then dissolved sufficiently, and then 10 equivalents of 9-BBN (9-Borabicyclononane) is added under argon atmosphere. Put and react at 40 ° C. After 2mL of 6M NaOH solution was added to the reaction to drop the temperature to room temperature. When the temperature drops to room temperature, ₂ mL of 33% aqueous H ₂ O ₂ is added and the temperature is raised to 40 ° C. to proceed with the reaction. After the reaction was terminated, the product was precipitated in a mixture of methanol and heavy water, extracted using a glass filter, and the methanol was removed using solvent extraction to remove the unreacted product. In this way, a poly (3-alkylthiophene) whose terminal is substituted with a hydroxy propyl group or a hydroxy ethyl group can be formed.

(2) Preparation of poly (3-alkylthiophene) having a halide group introduced at the terminal

Scheme 4

Methylene chloride dehydrated and degassed to replace the hydroxyl group of poly (3-alkylthiophene) having a hydroxyl group introduced at the end with a halide group (RX in the above scheme; X is Br or Cl, R is the remainder other than Br or Cl). Methylene chloride (MC) was dissolved in a poly (3-alkylthiophene) substituted with a hydroxypropyl group or a hydroxyethyl group at the end and sufficiently dissolved, and then triethylamine (TEA) was added under an argon atmosphere at 40 ° C. React. Thereafter, the compound into which the halide is introduced is injected and reacted at 40 ° C. After precipitation in methanol, the resultant was extracted using a glass filter, and then purified by washing with cold methanol (Cold MeOH). In this way, a poly (3-alkylthiophene) having a halide group introduced therein can be produced.

Preparation of Polythiophene Star Polymer Using Poly (3-alkylthiophene) Macro Initiator

Scheme 5

A crosslinking agent and a transition metal catalyst are added to the poly (3-alkylthiophene) macro initiator to polymerize the polythiophene star polymer in an oil bath maintained at a temperature of about 80 ° C. At this time, a ligand or an additive may be added as needed.

The present invention also provides a core comprising at least one selected from the group consisting of a homopolymer of a block copolymer divinyl monomer, a copolymer of divinyl monomer and a copolymer of divinyl monomer and vinyl monomer; And it relates to a polythiophene star polymer having an arm structure comprising a polythiophene of the following formula bonded to the core.

Wherein n is 0 to 12 and m is 1 to 90

The divinyl monomer serves as a crosslinking agent to bind the arm structure containing polythiophene, and is not particularly limited as long as it can form a core structure, for example, diacrylate, dimethacrylamide It may be at least one selected from the group consisting of diacrylamide, divinylphenyl, divinyl naphthalene, and divinyltoluene.

In addition, the vinyl monomers, for example, the vinyl monomers are styrene-based, butadiene-based, isoprene-based, methacryl-based, acrylic, acrylamide-based, methacrylamide-based, acrylonitrile, vinyl acetate, vinylpyridine and vinylpyrroli It may be one or more selected from the group consisting of money.

In one embodiment, the core comprising at least one selected from the group consisting of homopolymers of divinyl monomers, copolymers of divinyl monomers and copolymers of divinyl monomers and vinyl monomers, for example, Homopolymer, copolymer of two or more divinyl monomers, block copolymer of one divinyl monomer and one vinyl monomer, random copolymer of one divinyl monomer and one vinyl monomer, one kind of Random copolymer of divinyl monomer and two or more vinyl monomers, Random copolymer of one divinyl monomer and two or more vinyl monomer block copolymers, Random of two or more divinyl monomers and two or more vinyl monomers It may be at least one selected from the group consisting of a copolymer, and a random copolymer of a block copolymer of two or more divinyl monomers and two or more vinyl monomers.

Specific structures of the polythiophene star polymer including the core and having a polythiophene arm are shown in the following figure.

In another embodiment, the core may be a polythiophene is further bonded to a homopolymer or copolymer of one or more vinyl monomers. In this case, each of the structures of the polythiophene star polymer including the core and having a polythiophene arm to which a homopolymer, a block copolymer or a random copolymer of one or more vinyl monomers is further bonded, Same as the picture.

Such a polythiophene star polymer according to the present invention can be easily synthesized according to the present invention, and may be a three-dimensional polymer having various molecular weights of several tens to millions. The degree of polymerization of the polythiophene star polymer that can be produced is 1 to 90, and its molecular weight is not particularly limited, but may be, for example, tens of thousands to hundreds of thousands.

Hereinafter, the present invention will be described in more detail based on the following Examples and Experimental Examples, but the scope of the present invention is not limited thereto.

[Example]

1. Preparation of poly 3-hexylthiophene having an allyl group at the terminal

(1) Synthesis of 2,5-dibromo-3-hexylthiophene monomer

[Reaction Scheme 6]

Under 0.0012 equivalents of [1,3-bis (diphenylphosphine) propane] dichloronickel (II) (Ni (dppp) Cl ₂ ) catalyst, 1.3 equivalents of hexyl magnesium bromide (Hexyl-) was added to the monomer of 3-bromothiophene. MgBr) was added to synthesize 3-hexylthiophene, and then 2 equivalents of N-bromosuccimide (NBS) were added to synthesize 2,5-dibromo-3-hexylthiophene monomer.

(2) Preparation of poly (3-hexylthiophene) having an allyl group at the terminal

[Reaction Scheme 7]

The synthesized 2,5-dibromo-3-hexylthiophene monomer was dissolved in dehydrated and degassed THF, and then reacted with t-butyl-MgCl dissolved in dimethyl ether at room temperature under an argon atmosphere for 2 hours. Thereafter, 0.016 equivalents of Ni (dppp) Cl ₂ , which is a catalyst and an initiator, was added, and the reaction was performed at room temperature for about 10 minutes to polymerize poly (3-hexylthiophene).

In order to replace the allyl group at the terminal of the polymerized poly (3-hexylthiophene), about 0.2 equivalents of the Grignard reagent allylmagnesium bromide (Allyl-MgBr) reagent was added and reacted for about 2 minutes, followed by methanol. To terminate the polymerization. Synthesized poly (3-hexylthiophene) (P3HT) was precipitated in methanol, extracted using a glass filter, purified by solvent extraction using pentane to remove polymers of low molecular weight, and an allyl group was introduced at the terminal. Prepared P3HT.

2. Preparation of Poly (3-hexylthiophene) Macro Initiator

(1) Formation of (3-hexylthiophene) having a hydroxyl group introduced at the terminal

[Reaction Scheme 8]

In order to introduce a hydroxyl group into the terminal of P3HT whose terminal is substituted with an allyl group, P3HT having an allyl group is dissolved in dehydrated and degassed THF, and then sufficiently dissolved. Reaction was carried out for 24 hours. After 2mL of 6M NaOH solution was added and reacted for 15 minutes, the temperature was dropped to room temperature. When the temperature drops to room temperature, 2mL of 33% water-soluble H ₂ O ₂ was added, and the temperature was raised to 40 ° C. for 12 hours. After the reaction was terminated, the product was precipitated in a mixture of methanol and heavy water, extracted using a glass filter, and then the unreacted material was removed by solvent extraction using methanol.

(2) Preparation of poly (3-alkylthiophene) having ECPA introduced at the end

Scheme 9

In order to introduce an ECPA group at the terminal of the poly (3-alkylthiophene), poly (3-alkylthiophene) having a hydroxyl group at the terminal is sufficiently dissolved in dehydrated and degassed methylene chloride (MC), and then argon is sufficiently dissolved. TEA was added under an atmosphere and reacted at 40 ° C. for about 15 minutes. After the reaction, ECPA was injected drop by drop, and reacted at 40 ° C. for 12 hours to prepare poly (3-hexylthiophene) having an ECPA group introduced at the terminal. After precipitation in methanol, the resultant was extracted using a glass filter, and then purified by washing with cold methanol (Cold MeOH).

The structure of the resulting poly (3-hexylthiophene) macro initiator was analyzed by ¹ H NMR, and the analysis results are shown in FIG. 1.

In the ¹ H NMR analysis spectrum shown in FIG. 1, the CH peak (a) of poly (3-hexylthiophene) was detected at 7.09 to 6.97 ppm, and the CH ₂ peak of the hexyl group (b, c, d, e, f ) Was detected at 2.96-2.71 ppm, 1.851 ~ 1.662ppm, 1.599 ~ 1.299ppm, and CH ₃ (g) of hexyl group was detected at 1.052 ~ 0.877 ppm. CH ₂ (h) at the terminal of poly (3-hexylthiophene) was detected at 4.34-4.29 ppm, Cl-CH (i) peak of ECPA group was detected at 5.44-5.41 ppm, CH (j) of ECPA group , k) peaks were detected at 7.65 to 7.512 ppm and 7.512 to 7.39 ppm.

3. Preparation of Polythiophene Star Polymer Using Poly (3-hexylthiophene) Macro Initiator

[Reaction Scheme 10]

Ethylene glycol dimethacrylate, RuCl ₂ (PPh ₃ ) ₃ and tributylamine were added to the poly (3-hexylthiophene) macro initiator, dissolved with toluene, and maintained at a temperature of about 80 ° C. The polythiophene star polymer was polymerized in an oil bath.

In order to measure the degree of polymerization of the polythiophene star polymer, the conversion rate of the crosslinking agent over time, the reaction solution and the ¹ H NMR of the THF-GPC and the polythiophene star polymer of the polymerized polythiophene star polymer were measured as follows. .

(1) Measurement of conversion rate of crosslinking agent with time

The consumption of ethylene glycol dimethacrylate used as the crosslinking agent in the present example was measured according to the reaction time, and the conversion rate of the crosslinking agent was displayed with time. The conversion rate of the crosslinker with time is shown in FIG. 2.

2, it can be seen that the consumption of the crosslinking agent used for the polymerization of the polythiophene star polymer is increased. Thereby, the progress of polythiophene star polymer polymerization can be known. When the reaction time was 0 hours, that is, the conversion rate of the crosslinking agent was 0% before the reaction, the conversion rate of the crosslinking agent increased with the reaction time, and the conversion rate was 95% or more when the reaction time was 20 hours. That is, when the reaction time is 20 hours, it can be seen that the polymerization of the polythiophene star polymer is almost completed.

(2) Measurement of Gel Permission Chromatography (GPC)

The reaction solution (unreacted poly (3-hexylthiophene) macroinitiator, polymerized polythiophene star taken when the reaction time is 0, 5, 10 and 20 hours, respectively in the process of polymerizing the polythiophene star polymer) A solution containing a polymer, a transition metal compound, an additive, and the like) was measured by THF-GPC. The measured result is shown in FIG.

Referring to Figure 3, it can be seen that the molecular weight of the reaction solution increases as the reaction time increases. This is because the polythiophene star polymer having a high molecular weight was polymerized as the reaction proceeded. Since the polythiophene star polymer was not polymerized immediately before the reaction, a peak for the poly (3-hexylthiophene) macro initiator was detected between 30 and 36 minutes, and the molecular weight of the polythiophene star polymer was increased as the reaction time increased. By this increase, it can be seen that the peak for the polythiophene star polymer was detected in 24 to 30 minutes.

In addition, THF-GPC was measured for the reaction solution (solution without separating the polymerized polythiophene star polymer) after the polymerization reaction proceeded for 20 hours and the polythiophene star polymer separated from the reaction solution, respectively. The measurement results are shown in FIG. 4.

4, it can be seen that the polythiophene star polymer having a large molecular weight was measured by the preparation method according to the present embodiment.

(3) ¹ H NMR measurement of polythiophene star polymer

¹ H NMR was measured for the polythiophene star polymer produced in this example, and the measurement results are shown in FIG. 5.

In the ¹ H NMR analysis spectrum shown in FIG. 5, the CH peak (a) of the poly (3-hexylthiophene) branched of the polythiophene star polymer was detected at 7.09 to 6.97 ppm, and the CH ₂ peak of the hexyl group ( b, c, d, e, f) were detected at 2.96-2.71 ppm, 1.851-1.662 ppm, 1.599-1.299 ppm, and CH ₃ (g) of hexyl group was detected at 1.052-0.877 ppm.

However, since the core of a polythiophene star polymer is surrounded by the branch which consists of poly (3-hexylthiophene), it is difficult to measure by ¹ H NMR analysis. However, it can be seen from the THF-GPC measurement described above that a high molecular weight polythiophene star polymer was prepared.

Those skilled in the art to which the present invention pertains will be able to perform various applications and modifications within the scope of the present invention based on the above contents.

Claims (17)

Introducing a functional group at the polythiophene terminal of the formula to form a polythiophene macro initiator, wherein the functional group is Nitroxide-mediated polymerization (NMP), Reversible Addition-Fragmentation Chain Transfer (RAFT) or Atom Transfer Radical Polymerization (ATRP) A) a functional group capable of polymerization; And
Polymerizing the polythiophene star polymer by adding at least one divinyl monomer or at least one divinyl monomer and at least one vinyl monomer to the polythiophene macro initiator, wherein the divinyl monomer or vinyl monomer is NMP. (Nitroxide-mediated polymerization), RAFT (Reversible Addition-Fragmentation Chain Transfer) or ATRP (Atom Transfer Radical Polymerization) is a divinyl monomer or vinyl monomer capable of polymerization,
The polythiophene star polymer is a core comprising at least one selected from the group consisting of a homopolymer of divinyl monomers, a copolymer of divinyl monomers and a copolymer of divinyl monomers and vinyl monomers, A method for producing a polythiophene star polymer, characterized in that it has an arm structure containing polythiophene.

Wherein n is 0 to 12 and m is 1 to 90 The method of claim 1,
Forming the polythiophene macro initiator,
Forming an allyl group or vinyl group at the polythiophene end;
Introducing a hydroxyl group to the terminal of the polythiophene in which the allyl group or the vinyl group is formed; And
The hydroxyl group is a functional group capable of polymerizing ATRP (Atom Transfer Radical Polymerization), a halide compound, and benzyl 3-chloro-3-oxopropyl carbonotrithioate which is a functional group capable of polymerizing REVERsible Addition-Fragmentation Chain Transfer (RAFT) benzyl 3-chloro-3-oxopropyl carbonotrithioate), 2, 2, 5-trimethyl-4-phenyl-3-azahexane-3-oxy and 2-bromo-2 functional groups capable of polymerizing nitroxide-mediated polymerization (NMP) -Method for producing a polythiophene star polymer, characterized in that it comprises the step of substituting one selected from the group consisting of methyl propanoyl bromide. The method of claim 2,
The halide compound is 4-methylbenzyl bromide, 4-cyanobenzyl bromide, 4-bromobenzyl bromide, 2-bromopropionitrile, bromoacetonitrile, glycidol 2-bromopropionate, tert- Butyl 2-bromopropionate, hydroxyethyl 2-bromopropionate, vinyl chloroacetate, allyl chloroacetate, α-bromo-γ-butyrolactone, 2-chloroacetamide and ethyl-2-chloro Method for producing a polythiophene star polymer, characterized in that at least one compound selected from the group consisting of 2-phenyl acetate. The method of claim 2,
The polythiophene-terminated allyl group or vinyl group is formed by the Grignard metathesis method. delete The method of claim 1,
Polymerizing the polythiophene star polymer
Homopolymers of one or more vinyl monomers by polymerizing a polythiophene macroinitiator and at least one vinyl monomer by NMP (nitroxide-mediated polymerization) polymerization, reversible addition-fragmentation chain transfer (RAFT) polymerization or atom transfer radical polymerization (ATRP) polymerization, Preparing a polythiophene bonded to a block copolymer or a random copolymer; And
Method of producing a polythiophene star polymer comprising the step of further polymerizing the polythiophene and divinyl monomer or divinyl monomer and vinyl monomer to which the homopolymer, block copolymer or random copolymer of the vinyl monomer is bonded. The method of claim 1,
The divinyl monomers are divinyl monomers capable of polymerizing nitroxide-mediated polymerization (NMP), reversible addition-fragmentation chain transfer (RAFT) or atom transfer radical polymerization (ATRP), and are diacrylate-based, dimethacrylamide-based, and diacrylate-based monomers. A method for producing a polythiophene star polymer, which is at least one member selected from the group consisting of acrylamide, divinylphenyl, divinyl naphthalene, and divinyl toluene compounds. The method of claim 1,
The vinyl monomer is a vinyl monomer capable of nitroxide-mediated polymerization (NMP), reversible addition-fragmentation chain transfer (RAFT) or atom transfer radical polymerization (ATRP) polymerization, and may include styrene, butadiene, isoprene, methacryl, A method for producing a polythiophene star polymer, which is at least one selected from the group consisting of acryl, acrylamide, methacrylamide, acrylonitrile, vinyl acetate, vinylpyridine, and vinylpyrrolidone. The method of claim 2,
The hydroxyl group is substituted with a halide compound which is a functional group capable of ATRP (Atom Transfer Radical Polymerization) polymerization, and ATRP (Atom Transfer Radical Polymerization) polymerization of polythiophene star polymer is a transition metal catalyst CuX (X = Cl, Br) Method of producing a polythiophene star polymer is carried out including a. The method of claim 9,
Polythiophene star, which is performed by further adding at least one ligand selected from 2,2'-bipyruidine and its derivatives, 2-iminopyruidine and aliphatic polyamine to enable polymerization of the polythiophene star polymer. Method for producing a polymer. The method of claim 2,
The hydroxyl group is substituted with a halide compound, which is a functional group capable of ATRP (Atom Transfer Radical Polymerization) polymerization, and ATRP (Atom Transfer Radical Polymerization) polymerization of polythiophene star polymer is performed by RuCl ₂ (PPh ₃ ) ₃ , RuH ₂ ( Preparation of a polythiophene star polymer carried out comprising at least one transition metal catalyst selected from the group consisting of PPh ₃ ) ₃ , FeCl ₂ (PPh ₃ ) ₃ , NiBr ₂ (PPh ₃ ) ₃ and Ni (NCN) Br Way. The method of claim 11,
The polymerization of the polythiophene star polymer is carried out including the RuCl ₂ (PPh ₃ ) ₃ transition metal catalyst, and is further performed by adding at least one additive selected from the group consisting of tributylamine and dibutylamine. Method for producing a polymer. As a polythiophene star polymer prepared by claim 1,
A core comprising at least one selected from the group consisting of homopolymers of block copolymer divinyl monomers, copolymers of divinyl monomers and copolymers of divinyl monomers and vinyl monomers; And
Polythiophene star polymer having an arm structure comprising a polythiophene of the following formula bonded to the core.

Wherein n is 0 to 12 and m is 1 to 90 The method of claim 13,
The core
Homopolymers of divinyl monomers,
Copolymers of two or more divinyl monomers,
Block copolymer of one divinyl monomer and one vinyl monomer,
Random copolymer of one divinyl monomer and one vinyl monomer,
Random copolymer of one divinyl monomer and two or more vinyl monomers,
Random copolymer of one copolymer of divinyl monomers and two or more types of vinyl monomers,
At least one polythiophene star selected from the group consisting of random copolymers of two or more divinyl monomers and two or more vinyl monomers, and random copolymers of two or more divinyl monomers and block copolymers of two or more vinyl monomers. Polymer. The method of claim 13,
The divinyl monomer is at least one polythiophene star polymer selected from the group consisting of diacrylate-based, dimethacrylamide-based, diacrylamide-based, divinylphenyl-based, divinyl naphthalene-based, and divinyltoluene-based compounds. . The method of claim 13,
The vinyl monomer is one selected from the group consisting of styrene, butadiene, isoprene, methacryl, acrylic, acrylamide, methacrylamide, acrylonitrile, vinyl acetate, vinylpyridine and vinylpyrrolidone. The above polythiophene star polymer. The method of claim 13,
Polythiophene star polymer, characterized in that the polythiophene is further bonded to a homopolymer, a block copolymer or a random copolymer of one or more vinyl monomers.

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