KR102071914B1 - Block copolymer - Google Patents

Abstract

In the present application, a block copolymer and its use may be provided. Block copolymer of the present application is excellent in self-assembly can be effectively applied in various applications.

Description

Block Copolymer {BLOCK COPOLYMER}

The present application relates to a block copolymer and its use.

The block copolymer has a molecular structure in which polymer segments having different chemical structures are connected through covalent bonds. The block copolymer may form a periodically arranged structure such as a sphere, a cylinder, or a lamella by phase separation. The size of the domain of the structure formed by the self-assembly of the block copolymer can be controlled in a wide range, it is possible to manufacture a variety of forms of the structure of various next generation nano such as high-density magnetic storage medium, nanowire fabrication, quantum dots or metal dots It can be applied to pattern formation by an element, a magnetic recording medium or lithography.

The present application provides a block copolymer and its use.

As used herein, unless otherwise specified, the term alkyl group may mean an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The alkyl group may be a straight chain, branched or cyclic alkyl group, and may be optionally substituted with one or more substituents.

As used herein, unless otherwise specified, the term alkoxy group may mean an alkoxy group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The alkoxy group may be a straight chain, branched or cyclic alkoxy group, and may be optionally substituted with one or more substituents.

As used herein, unless otherwise specified, the term alkylene group may mean an alkylene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The alkylene group may be a straight chain, branched or cyclic alkylene group, and may be optionally substituted with one or more substituents.

As used herein, the term alkenylene group or alkynylene group is an alkenylene group or alkynylene having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms unless otherwise specified. Can mean a group. The alkenylene group or alkynylene group may be linear, branched or cyclic, and may be optionally substituted with one or more substituents.

In the present application, as the substituent which may be optionally substituted with an alkyl group, an alkylene group, an alkenylene group, an alkynylene group or an alkoxy group, a hydroxy group, a halogen atom, a carboxyl group, a glycidyl group, an acryloyl group, a methacryloyl group, Acryloyl group oxy, methacryloyl group oxy group, thiol group, alkyl group, alkenyl group, alkynyl group, alkylene group, alkenylene group, alkynylene group, alkoxy group or aryl group may be exemplified, but is not limited thereto. no.

Exemplary block copolymers of the present application may include a polymer segment having a unit represented by Formula 1 below. Hereinafter, in the present specification, the polymer segment may be referred to as segment A. The polymer segment A may include the unit as a main component. In the present specification, that a segment includes a unit as a main component means that the ratio of the unit in the segment is 55% by weight, 60% by weight, 75% by weight, 80% by weight, 85% by weight, 90% by weight. It may refer to the case of more than or equal to 95% by weight and less than or equal to 100% by weight.

[Formula 1]

In Formula 1, R1 is hydrogen or an alkyl group, R2 is an alkyl group or -L1-C (= 0) -N (R3) -L2-C (= 0) -O-R4, wherein L1 and L2 are each independently It is an alkylene group, R <3> and R <4> may be respectively independently hydrogen or an alkyl group.

R 1 in Formula 1 is hydrogen or an alkyl group having 1 to 4 carbon atoms in another example; Hydrogen or methyl group; Or a methyl group.

In addition, in Formula 1, R2 may be, in another example, an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms.

In Formula 1, when R2 is -L1-C (= 0) -N (R3) -L2-C (= 0) -O-R4, L1 and L2 are each independently alkyl having 1 to 4 carbon atoms. R3 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R4 may be a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

The polymer segment A contains the unit as a main component, and if necessary, may include other known monomer units within a range that does not impair the effect of the block copolymer.

The block copolymer may comprise a polymer segment A together with another polymer segment. In the present specification, the segment may be referred to as segment B.

In the present application, any two kinds of polymer segments are identical to each other if the kind of monomer units included as a main component of two kinds of polymer segments are identical to each other or the kind of monomer units included in any two kinds of polymer segments is 50%. Or more, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more or 90% or more in common, and the variation in the weight ratio of the common monomer unit of each polymer segment Within 30%, within 25%, within 20%, within 20%, within 15%, within 10%, or within 5%. The monomer unit included in the polymer segment as a main component is 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more or 90% or more by weight in the polymer segment. And a monomer unit contained at 100% or less. If both polymer segments do not satisfy both cases, they are different polymer segments from each other. It may be appropriate that the proportion of monomer units in common is satisfied for both polymer segment modes. For example, if one polymer segment 1 has monomer units of A, B, C, D and F and another polymer segment 2 has monomer units of D, F, G and H, Common monomer units are D and F. Since the polymer segment 1 has two types of all five monomers in common, the common ratio is 40% (= 100 × 2/5), but the polymer segment 2 has the above ratio. Is 50% (= 100 x 2/5). Therefore, in this case, since the common ratio is 50% or more only in the polymer segment 2, it can be recognized that both polymer segments are not the same. In addition, the deviation of the weight ratio of a common monomer is the percentage of the value which divided the numerical value which subtracted the small weight ratio from the large weight ratio by the small weight ratio. For example, in this case, the weight ratio of the D monomer units of Segment 1 is about 40% based on 100% of the total weight ratio of the total monomer units of Segment 1, and the weight ratio of the D monomer units of Segment 2 is the total of Segment 2 If it is about 30% based on 100% of the total weight ratio of the monomer units, the weight ratio deviation may be about 33% (= 100 × (40-30) / 30). If two or more kinds of monomer units are common in two segments, the same segment is referred to as a common monomer if less than 30% of the above-described weight ratio deviation is satisfied for all common monomers, or is satisfied for the main monomer unit. Can be considered. Each polymer segment recognized as being identical by the above criteria may be a polymer of a different form (eg, one segment is in the form of a block copolymer and the other is in the form of a random copolymer), Suitably the same type of polymer.

The polymer segment B may include, for example, a unit represented by Formula 2 below. Segment B may include a unit of Formula 2 as a main component.

[Formula 2]

X2 in Formula 2 is a single bond, an oxygen atom, a sulfur atom, -S (= O) 2-, an alkylene group, an alkenylene group or an alkynylene group, and R1 to R5 are each independently hydrogen, a halogen atom, an alkyl group or An alkoxy group, at least one of R 1 to R 5 in Formula 2 is an alkyl group having 10 to 18 carbon atoms or an alkoxy group having 10 to 18 carbon atoms.

X2 in Formula 2 may be, in another example, a single bond or an oxygen atom, or a single bond, but is not limited thereto.

R 1 to R 5 in Formula 2 each independently represent a hydrogen, a halogen atom, an alkyl group or an alkoxy group, and at least one of R 1 to R 5 in Formula 2 is an alkyl group having 10 to 18 carbon atoms or an alkoxy group having 10 to 18 carbon atoms.

In one example, R 1, R 2, R 4 and R 5 in R 1 to R 5 are each independently hydrogen, a halogen atom or an alkyl group having 1 to 8 carbon atoms; Or hydrogen, a halogen atom or an alkyl group having 1 to 4 carbon atoms; Or hydrogen or a halogen atom, and R 3 may be an alkyl group having 10 to 18 carbon atoms or an alkoxy group having 10 to 18 carbon atoms.

Halogen atoms that can be applied above include, but are not limited to, a chlorine atom or a fluorine atom.

In the unit of Formula 2, the number of halogen atoms included in R 1 to R 5 may be, for example, one or more, two or more, three or more, or four or more. These halogen atoms may be 20 or less, 15 or less, 10 or less, 8 or less, or 6 or less.

The block copolymer including the polymer segments A and B as described above may exhibit excellent self-assembly or phase separation characteristics.

The block copolymer may be in the form of a diblock copolymer including only the polymer segments A and B or a multiblock copolymer of diblock or more including additional polymer segments in a range that does not impair the effect of the block copolymer. Examples of the segment that may be further included include polystyrene such as polyvinylpyrrolidone polymer segment, polylactic acid polymer segment, polyvinylpyridine polymer segment, polystyrene or poly trimethylsilylstyrene, and the like. Polymer segments, polyalkylene oxide polymer segments such as polyethylene oxide, poly butadiene polymer segments, poly isoprene polymer segments, or polyolefin polymer segments such as polyethylene It is possible, but is not limited to this.

When the block copolymer of the present application is in the form of a diblock copolymer, the volume fraction of the polymer segment A may be in the range of 0.1 to 0.9, and the sum of the volume fractions of the polymer segments A and B may be 1.

The method for producing the block copolymer of the present application is not particularly limited as long as it includes the step of forming at least one polymer segment of the block copolymer using monomers capable of forming the desired polymer segment.

For example, the block copolymer may be prepared by LRP (Living Radical Polymerization) method using the monomer. For example, an anionic polymerization or an organic alkali metal compound synthesized in the presence of an inorganic acid such as an alkali metal or a salt of an alkaline earth metal is polymerized using an organic rare earth metal complex as a polymerization initiator or an organic alkali metal compound as a polymerization initiator. Anion polymerization method synthesized in the presence of an organoaluminum compound using as an initiator, atom transfer radical polymerization method (ATRP) using an atom transfer radical polymerization agent as a polymerization control agent, an atom transfer radical polymerization agent as a polymerization control agent is used. Activators Regenerated by Electron Transfer (ARRP) Atomic Radical Polymerization (ATRP), Initiators for continuous activator regeneration (ICAR), and Reversible Addition of Inorganic Reductants Reversible addition-cleavage chain transfer using cleavage chain transfer agents And a method using the polymerization method of (RAFT) or an organic tellurium compound, etc. as an initiator, may be subject to a suitable method among these methods is selected.

For example, the block copolymer can be prepared in a manner that comprises polymerizing a reactant comprising monomers capable of forming the polymer segment by living radical polymerization in the presence of a radical initiator and a living radical polymerization reagent. have.

The method of forming another polymer segment included in the copolymer together with the polymer segment formed by using the monomer in the preparation of the block copolymer is not particularly limited, and an appropriate monomer is selected in consideration of the type of the desired polymer segment. To form the other polymer segment.

The manufacturing process of the polymer segment copolymer may further include, for example, precipitating the polymerization product produced through the above process in the non-solvent.

The kind of radical initiator is not particularly limited and may be appropriately selected in consideration of the polymerization efficiency. For example, azobisisobutyronitrile (AIBN) or 2,2'-azobis-2,4-dimethylvaleronitrile (2,2 ') can be appropriately selected. Azo compounds such as -azobis- (2,4-dimethylvaleronitrile)) and peroxides such as benzoyl peroxide (BPO) or di-t-butyl peroxide (DTBP) can be used.

Living radical polymerization processes are, for example, methylene chloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, acetone, chloroform, tetrahydrofuran, dioxane, monoglyme, diglyme, dimethylform It may be carried out in a solvent such as amide, dimethyl sulfoxide or dimethylacetamide.

As the non-solvent, for example, alcohols such as methanol, ethanol, normal propanol or isopropanol, glycols such as ethylene glycol, ether series such as n-hexane, cyclohexane, n-heptane or petroleum ether may be used. It is not limited to this.

Since the block copolymer includes two or more polymer chains connected by covalent bonds, phase separation occurs. The block copolymer of the present application exhibits excellent phase separation characteristics, and may form a nanoscale structure by microphase seperation as needed. The shape and size of the nanostructure may be controlled by the size (molecular weight, etc.) of the block copolymer, the relative ratio between the polymer segments, and the like. As the structure formed by phase separation, spherical, cylinder, gyroid, lamellae and inverted structures can be exemplified, and the ability of the block copolymer to form such a structure can be referred to as self-assembly.

The number average molecular weight (Mn) of the block copolymer may be, for example, in the range of 1,000 to 200,000. As used herein, the term number average molecular weight is a conversion value with respect to standard polystyrene measured using a gel permeation chromatograph (GPC), and the term molecular weight herein refers to a number average molecular weight unless otherwise specified. In another example, the molecular weight (Mn) may be, for example, 3000 or more, 5000 or more, 7000 or more, 9000 or more, 11000 or more, 13000 or more, or 15000 or more. In another example, the molecular weight (Mn) may be about 180000 or less, 160000 or less, 140000 or less, 120000 or less, 100000 or less, 90000 or less, 80000 or less, 70000 or less, 60000 or less, 50000 or less, 40000 or less, 30000 or less or about 25000 or less. . The block copolymer may have a dispersion degree (polydispersity, Mw / Mn) in the range of 1.01 to 1.60. The dispersity may in another example be at least about 1.1, at least about 1.2, at least about 1.3 or at least about 1.4.

In this range, the block copolymer may exhibit suitable self-assembly properties. The number average molecular weight and the like of the block copolymer can be adjusted in view of the desired self-assembly structure and the like.

When the block copolymer includes at least the polymer segments A and B, the ratio of the polymer segment A in the block copolymer may be in the range of 10 mol% to 90 mol%.

The present application also relates to a polymer membrane comprising the block copolymer. The polymer film may be used in various applications, and for example, may be used in various electronic or electronic devices, a process of forming the pattern or a recording medium such as a magnetic storage recording medium, a flash memory, or a biosensor.

In one example, the block copolymer in the polymer membrane may implement a periodic structure including a sphere, a cylinder, a gyroid or a lamellar through self-assembly. .

For example, within the segment of the polymer segment A or B or other polymer segment covalently bonded to the block copolymer, the other segment may form a regular structure such as lamellar form or cylinder form.

The present application also relates to a method of forming a polymer film using the block copolymer. The method may include forming a polymer film including the block copolymer on a substrate in a self-assembled state. For example, the method may include forming a block copolymer or a layer of a coating liquid diluted in a suitable solvent on a substrate by applying, and if necessary, aged or heat-treated the layer.

The aging or heat treatment may be performed based on, for example, the phase transition temperature or the glass transition temperature of the block copolymer, and may be performed, for example, at a temperature above the glass transition temperature or the phase transition temperature. The time for which such heat treatment is performed is not particularly limited, and for example, it may be performed in the range of about 1 minute to 72 hours, but this may be changed as necessary. In addition, the heat treatment temperature of the polymer thin film may be, for example, about 100 ° C to 250 ° C, but this may be changed in consideration of the block copolymer used.

The formed layer may, in another example, be solvent aged for about 1 minute to 72 hours in a nonpolar solvent and / or a polar solvent at room temperature.

The present application also relates to a pattern forming method. The method selectively removes the first or polymer segment B of the block copolymer, for example, from a laminate having a substrate and a polymer film formed on the surface of the substrate and comprising the self-assembled block copolymer. It may include the process of. The method may be a method of forming a pattern on the substrate. For example, the method may include forming a polymer film comprising the block copolymer on the substrate, and selectively etching any one or more polymer segments of the block copolymer present in the film, followed by etching the substrate. have. In this way, for example, formation of nanoscale fine patterns is possible. In addition, according to the shape of the block copolymer in the polymer film, it is possible to form various types of patterns such as nanorods or nanoholes through the above method. If necessary, the block copolymer and another copolymer or homopolymer may be mixed to form a pattern. The kind of the substrate to be applied in this manner is not particularly limited, and may be selected as necessary, for example, silicon oxide or the like may be applied.

For example, this approach can form nanoscale patterns of silicon oxide that exhibit high aspect ratios. For example, after forming the polymer film on silicon oxide and selectively removing any polymer segment of the block copolymer in a state in which the block copolymer in the polymer film has a predetermined structure, silicon oxide is removed in various ways, for example. For example, various forms including nanorods or patterns of nano holes may be realized by etching by reactive ion etching. In addition, it may be possible to implement a nanopattern with a high aspect ratio through this method.

For example, the pattern may be implemented on a scale of several tens of nanometers, and the pattern may be utilized for various applications including, for example, a magnetic recording medium for next generation information electronics.

The method of selectively removing any polymer segment of the block copolymer in the above method is not particularly limited, and for example, irradiating an appropriate electromagnetic wave, for example, ultraviolet rays, to the polymer membrane to remove the relatively soft polymer segment. Can be used. In this case, UV irradiation conditions are determined according to the type of the polymer segment of the block copolymer, for example, it can be carried out by irradiating ultraviolet light of about 254 nm wavelength for 1 minute to 60 minutes.

In addition, after the ultraviolet irradiation, the polymer film may be treated with an acid or the like to further remove the segment decomposed by the ultraviolet ray.

In addition, the step of selectively etching the substrate using the polymer film from which the polymer segment has been removed is not particularly limited, and may be performed through, for example, a reactive ion etching step using CF 4 / Ar ions, and the like. Subsequently, the step of removing the polymer film from the substrate by oxygen plasma treatment or the like may also be performed.

In the present application, block copolymers and uses thereof may be provided. Block copolymer of the present application is excellent in self-assembly can be effectively applied in various applications.

1 to 3 is a photograph of the polymer structure expressed in the Examples.

Hereinafter, the present application will be described in more detail with reference to Examples and Comparative Examples according to the present application, but the scope of the present application is not limited to the examples given below.

1. NMR measurement method

NMR analysis of each compound of the preparation was carried out using an NMR spectrometer comprising a Varian Unity Inova (500 MHz) spectrometer with triple resonance 5 mm probe at room temperature. In the NMR measurement, each compound was dissolved in a concentration of about 10 mg / ml in a solvent for NMR measurement (CDCl 3), and chemical shifts were expressed in ppm.

<Applicable abbreviation>

br = wide signal, s = singlet, d = doublet, dd = doublet, t = triplet, dt = doublet, q = quartet, p = quintet, m = multiplet.

2.Gel Permeation Chromatograph

The number average molecular weight (Mn) and the molecular weight distribution were measured using gel permeation chromatography (GPC), and the measurement conditions are as follows.

<GPC measurement condition>

Instrument: 1200 series by Agilent technologies

Column: Use 2 PLgel mixed B of Polymer Laboratories

Solvent: THF

Column temperature: 35 ° C

Sample concentration: 1mg / mL, 200L injection

Standard sample: Polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485)

The block copolymer prepared in Example or Comparative Example is placed in a 5 mL vial and diluted with THF to 1 mg / mL. Then, the standard sample for calibration and the sample to be analyzed were filtered through a syringe filter (pore size: 0.45 μm) and measured. The analytical program used ChemStation of Agilent Technologies, and the weight average molecular weight (Mw) and number average molecular weight (Mn) were obtained by comparing the elution time of the sample with the calibration curve by GPC, and then the molecular weight from the ratio (Mw / Mn) Distribution (PDI) was calculated.

Preparation Example 1 Synthesis of DTFS

4-dodecyloxytetrafluorostyrene (DTFS) was synthesized in the following manner. 1-dodecanol (31.0 g, 168 mmol) was placed in a flask and dissolved in 500 mL of THF (tetrahydrofuran). The flask was immersed in an ice bath, with stirring slightly added sodium hydride (6.2 g, 142 mmol) and slowly added pentafluoro styrene (23.0 g, 129 mmol). The flask was placed at room temperature and allowed to react overnight. After the reaction, spherical components were removed by a filter, and the remaining liquid phase was collected and purified by column chromatography using a methylene chloride / hexane mixed solution as a mobile phase.The solvent was removed from the obtained solution, stirred in vacuo and the unreacted reactant was removed. A colorless liquid DTFS was prepared (24.4 g, 67.7 mmol, 52%).

<NMR analysis result>

1 H-NMR (CDCl 3): δ 6.63 (dd, 1 H); δ 6.02 (d, 1H); δ 5.82 (d, 1H); delta 4.21 (t, 2H); δ 1.79 (tt, 2H); δ 1.45 (tt, 2H); δ 1.35-1.20 (m, 16H); δ 0.88 (t, 3H).

Preparation Example 2 Synthesis of BOAOM

2-((2-butyloxy) -2-oxoethyl) amino-2-oxoethyl methacrylate) (BOAOM, in formula 1, R1 is methyl group, R2 is -L1-C (= O) -N (R3) -L2-C (= O) -O-R4, wherein L1 and L2 are ethylene groups, R3 is a hydrogen atom, and R4 is a butyl group) was synthesized in the following manner. Boc-glycine (15.0 g, 85.6 mmol) and 1-butanol (7.6 g, 102.7 mmol) were added to the flask, dissolved in methylene chloride (400 mL), and then DCC (N, N'-dicylcohexylcarbodiimide) (21.2 g, 102.7 mmol). ) And DMAP (p-dimethylaminopyridine) (4.2 g, 34.2 mmol) were added and reacted at room temperature overnight. After the reaction, the solid was removed by filtration, and the column was purified by ethyl acetate / hexane mixed solution to obtain a colorless liquid product (butyl 2-((tert-butoxycarbonyl) amino) acetate). The product was placed in a flask as it was, dissolved in 1,4-dioxane (140 mL), and then reacted overnight at room temperature by adding HCL solution (4N in 1,4-dioxane, 70 mL, excess). After completion of the reaction, the solvent was removed, and column purification with ethyl acetate / hexane solution to give a viscous colorless liquid intermediate (2-butoxy-2-oxoethanaminium chloride).

<NMR analysis result>

1 H-NMR (DMSO-d 6): δ 8.53 (s, 3H); delta 4.14 (t, 2H); delta 3.75 (s, 2H); δ 1.57 (m, 2H); δ 1.34 (m, 2H); δ 0.99 (t, 3H)

The above intermediate was placed in a flask as it was, dissolved in methylene chloride (300 mL), the flask was then placed in an ice bath, and chloroacetyl chloride (19.3 g, 171 mmol) was added while stirring. Triethyl amine (25.9 g, 256 mmol) was slowly added to the reaction solution, and the flask was kept at room temperature overnight. After the reaction, the solids were removed by a filter, and the column was purified by ethyl acetate / hexane solution to obtain a second liquid intermediate (butyl 2- (2-chloroacetamido) acetate) (13.9 g, 66.9 mmol).

<NMR analysis result>

1 H-NMR (CDCl 3): δ 7.11 (s, 1 H); δ 4.18 (t, 2H); delta 4.09 (s, 2H); delta 4.07 (d, 2H); δ 1.63 (tt, 2H); δ 1.37 (m, 2H); δ 0.93 (t, 3H)

The second intermediate (13.9 g, 66.9 mmol) and methacrylic acid (11.5 g, 133.9 mmol) were added to the flask, stirred and dissolved in DMF (150 mL), followed by potassium carbonate (27.8 g, 200.8 mmol) and potassium iodide. Id (1.11 g, 6.69 mmol) was added. The mixture was reacted at about 80 ° C. for 2 hours, poured into excess ice water, precipitated and extracted with diethyl ether. The organic layers were combined, dried over anhydrous magnesium sulfate, and the solvent was removed. Column purification with ethyl acetate / hexanes solution and recrystallization gave the white solid target product (BOAOM) (8.6 g, 33.4 mmol).

<NMR analysis result>

1 H-NMR (CDCl 3): δ 6.66 (s, 1 H); delta 6.24 (s, 2H); δ 5.71 (s, 1 H); delta 4.70 (s, 2H); δ 4.18 (t, 2H); delta 4.10 (d, 2H); δ 1.64 (tt, 2H); δ 1.38 (m, 2H); δ 0.94 (t, 3H)

Example 1:

2 g of monomer (BOAOM) of Preparation Example 2, 8.0 mg of AIBN (Azobisisobutyronitrile), 21.5 mg of CPBD (2-Cyano-2-propyl benzodithioate) as a RAFT agent ((Reversible Addition-Fragmentation chain Transfer agent), 8.040 mL of anisole The mixture was placed in a flask, stirred for 1 hour at room temperature under a nitrogen atmosphere, and then subjected to RAFT polymerization for about 4 hours in a silicon oil vessel at 70 ° C. After polymerization, the reaction solution was precipitated twice in 300 mL of ether, followed by filtration under reduced pressure. Thus, a large initiator (number average molecular weight Mn: 14,400, molecular weight distribution PDI: 1.26) having a RAFT reagent bound to a BOAOM polymer (PBOAOM) terminal was synthesized.

1.051 g of monomer (DTFS) of Preparation Example 1, 0.35 g of the synthesized macroinitiator, 2.0 mg of AIBN (Azobisisobutyronitrile) was dissolved in 3.285 mL of anisole in a flask, and stirred at room temperature under nitrogen atmosphere for 1 hour, followed by 70 ° C of The RAFT polymerization reaction was carried out in a silicone oil container for about 4 hours. After the polymerization reaction, the reaction solution was precipitated twice in 250 mL of methanol, followed by filtration under reduced pressure to prepare a target block copolymer (number average molecular weight Mn: 51,300, molecular weight distribution PDI: 1.25). The block copolymer includes polymer segment A derived from the monomer of Preparation Example 2 and polymer segment B derived from the monomer of Preparation Example 1. In the above, the volume fraction of the polymer segment A was about 0.4, and the volume fraction of the polymer segment B was about 0.6.

Example 2:

2 g of methyl methacrylate, 15.6 mg of Azobisisobutyronitrile (AIBN), 42.0 mg of 2-BD-cyano-2-propyl benzodithioate (RBD) (Reversible Addition-Fragmentation Chain Transfer Agent) and 2.01 mL of anisole were added to the flask. After stirring for 1 hour at room temperature under a nitrogen atmosphere, the RAFT polymerization reaction was performed for about 4 hours in a silicone oil vessel at 70 ° C. After the polymerization reaction, the reaction solution was precipitated in 300 mL of methanol, and then filtered under reduced pressure to obtain the RAFT reagent from the MMA polymer. A macroinitiator (number average molecular weight Mn: 8,500, molecular weight distribution PDI: 1.15) bound to the (poly (methylmethacrylate)) terminal was synthesized.

2.544 g of monomer (DTFS) of Preparation Example 1, 0.3 g of the synthesized macroinitiator, and 2.9 mg of AIBN (Azobisisobutyronitrile) were dissolved in 6.669 mL of anisole in a flask, and stirred at room temperature under nitrogen atmosphere for 1 hour, followed by 70 ° C of The RAFT polymerization reaction was performed for about 6 hours in a silicone oil vessel. After the polymerization reaction, the reaction solution was precipitated twice in 250 mL of methanol, and then filtered under reduced pressure to prepare a target block copolymer (number average molecular weight Mn: 38,500, molecular weight distribution PDI: 1.16). The block copolymer includes polymer segment A derived from methyl methacrylate and polymer segment B derived from monomer of Preparation Example 1. In the above, the volume fraction of the polymer segment A was about 0.3, and the volume fraction of the polymer segment B was about 0.7.

Example 3:

1 g of Tert-butyl methacrylate, 2.3 mg of AIBN (Azobisisobutyronitrile), 15.6 mg of CPBD (2-Cyano-2-propyl benzodithioate) (Reversible Addition-Fragmentation chain Transfer agent), 1.01 mL of anisole After stirring for 1 hour at room temperature under a nitrogen atmosphere, the RAFT polymerization reaction was performed for about 12 hours in a silicon oil vessel at 70 ° C. After the polymerization reaction, the reaction solution was precipitated in 300 mL of methanol, and then filtered under reduced pressure to obtain the RAFT reagent. A macroinitiator (number average molecular weight Mn: 8,400, molecular weight distribution PDI: 1.14) bound to the tBMA polymer (PtBMA) terminal was synthesized.

1.716 g of Monomer (DTFS) of Preparation Example 1, 0.2 g of the synthesized macroinitiator, 2.0 mg of AIBN (Azobisisobutyronitrile) were dissolved in 4.493 mL of anisole in a flask, and stirred at room temperature under nitrogen atmosphere for 1 hour, followed by 70 ° C of The RAFT polymerization reaction was performed for about 6 hours in a silicone oil vessel. After the polymerization reaction, the reaction solution was precipitated twice in 250 mL of methanol, followed by filtration under reduced pressure to prepare a target block copolymer (number average molecular weight Mn: 25,600, molecular weight distribution PDI: 1.2). The block copolymer includes polymer segment A derived from tert-butyl methacrylate and polymer segment B derived from the monomer of Preparation Example 1. In the above, the volume fraction of the polymer segment A was about 0.4, and the volume fraction of the polymer segment B was about 0.6.

Test Example 1. Confirmation of Self Assembly Pattern

The coating solution obtained by diluting the block copolymer synthesized in Example 1, 2, or 3 to an appropriate concentration in toluene was coated on the silicon wafer substrate at a speed of 3000 rpm for 60 seconds using a spin coater to form a polymer thin film. The thin film was heat-treated at 160 ° C. for 1 hour to express nanostructures on the surface of the thin film. 1 to 3 are images of the structures expressed for Examples 1 to 3, respectively. From the figure, it can be seen that an appropriate phase separation structure was found, and in particular, the case of Example 1 showed an excellent phase separation structure compared to other examples.

Claims (10)

A block copolymer comprising a polymer segment A having a unit represented by Formula 1 and a polymer segment B having a unit represented by Formula 2 below:
[Formula 1]

[Formula 2]

In formula (1), R1 is hydrogen or an alkyl group, R2 is an alkyl group or -L1-C (= 0) -N (R3) -L2-C (= 0) -O-R4, wherein L1 and L2 are each independently Is an alkylene group, R3 and R4 are each independently hydrogen or an alkyl group, and in the formula (2), X2 is a single bond, an oxygen atom, a sulfur atom, -S (= 0) 2-, an alkylene group, an alkenylene group or an alkynylene group R 1 to R 5 each independently represent a hydrogen, a halogen atom, an alkyl group or an alkoxy group, and at least one of R 1 to R 5 in Formula 2 is an alkoxy group having 10 to 18 carbon atoms. The compound of claim 1, wherein in Formula 1, R2 is -L1-C (= 0) -N (R3) -L2-C (= 0) -O-R4, wherein L1 and L2 are each independently 1 to 4 is an alkylene group, R 3 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 4 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. The block copolymer of claim 1, wherein X 2 in Formula 2 is a single bond or an oxygen atom. The block copolymer according to claim 1, wherein in the formula (2), R 1 to R 5 contain three or more halogen atoms. delete The block copolymer of claim 1, wherein the polymer segment is in a diblock form including only polymer segments A and B. The block copolymer according to claim 1, wherein the volume fraction of the polymer segment A is in the range of 0.1 to 0.9, and the sum of the volume fractions of the polymer segments A and B is 1. A polymer membrane comprising the self-assembled block copolymer of claim 1. A method of forming a polymer film comprising forming a polymer film comprising the block copolymer of claim 1 on a substrate. Selectively removing a polymer segment A or a polymer segment different from the polymer segment A of the block copolymer from a laminate having a substrate and a polymer film formed on the substrate and comprising the self-assembled block copolymer of claim 1 Pattern forming method comprising the step of.

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