KR20150066489A - Block copolymer - Google Patents

Abstract

The present invention can provide a block copolymer and a use thereof. The block copolymer of the present invention has an excellent self-assembly property, and thus can be effectively applied to various uses. The block copolymer comprises a first block.

Description

BLOCK COPOLYMER < RTI ID = 0.0 >

This application relates to block copolymers and uses thereof.

The block copolymer has a molecular structure in which polymer blocks having different chemical structures are linked via covalent bonds. The block copolymer can 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-assembling phenomenon of the block copolymer can be widely controlled, and various types of structures can be manufactured. Thus, various next-generation nano-structures such as high density magnetic storage media, nanowire fabrication, And can be applied to pattern formation by devices, magnetic recording media, lithography, or the like.

The present application provides block copolymers and uses thereof.

As used herein, 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, unless otherwise specified. The alkyl group may be a straight chain, branched or cyclic alkyl group and may be optionally substituted by 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 groups may be straight, branched or cyclic alkoxy groups and may optionally be substituted by one or more substituents.

As used herein, the term alkenyl or alkynyl group means an alkenyl group or alkynyl group 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 do. The alkenyl or alkynyl group may be linear, branched or cyclic and may optionally be substituted by one or more substituents.

As used herein, unless otherwise specified, the 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, branched or cyclic alkylene group and may optionally be substituted by one or more substituents.

As used herein, the term alkenylene group or alkynylene group means an alkenylene group or an alkynylene group 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, It can mean a group. The alkenylene or alkynylene group may be linear, branched or cyclic and may optionally be substituted by one or more substituents.

As used herein, the term "aryl" group or "arylene group" means, unless otherwise specified, one benzene ring structure, two or more benzene rings connected together sharing one or two carbon atoms, Or a monovalent or di-valent residue derived from a compound or a derivative thereof.

The aryl group or the arylene group may be, for example, an aryl group having 6 to 30 carbon atoms, 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 13 carbon atoms unless otherwise specified.

The term aromatic structure in this application may mean the aryl group or the arylene group.

As used herein, the term alicyclic ring structure means a cyclic hydrocarbon structure other than an aromatic ring structure unless otherwise specified. The alicyclic ring structure may be, for example, an alicyclic ring structure having 3 to 30 carbon atoms, 3 to 25 carbon atoms, 3 to 21 carbon atoms, 3 to 18 carbon atoms, or 3 to 13 carbon atoms unless otherwise specified .

The term single bond in the present application may mean that no separate atom is present at the site. For example, in the structure represented by A-B-C, when B is a single bond, it may mean that no atom exists at a site represented by B and A and C are directly connected to form a structure represented by A-C.

Examples of the substituent which may optionally be substituted in the present application include an alkyl group, an alkenyl group, an alkynyl group, an alkylene group, an alkenylene group, an alkynylene group, an alkoxy group, an aryl group, an arylene group, a linear chain or an aromatic structure, An alkenyl group, an alkynylene group, an alkenyl group, an alkynyl group, an alkenyl group, an alkynyl group, an alkynyl group, an alkenyl group, an alkynyl group, An alkoxy group, an aryl group, and the like, but the present invention is not limited thereto.

Exemplary block copolymers of the present application may include blocks represented by the following general formula (1).

[Chemical Formula 1]

In formula (1), X ₂ represents a single bond, an oxygen atom, a sulfur atom, -S (═O) ₂ -, an alkylene group, an alkenylene group or an alkynylene group, each of R ₁ to R ₅ independently represents hydrogen, To 8 carbon atoms, or a straight chain having at least 9 chain forming atoms, and at least one of R ₁ to R ₅ is a straight chain having 9 or more chain forming atoms.

In another embodiment, X ₂ in the formula (1) may be a single bond or an oxygen atom, or may be a single bond, but is not limited thereto.

In formula (1), R ₁ to R ₅ are each independently hydrogen, an alkyl group having 1 to 8 carbon atoms, or a straight chain having at least 9 chain-forming atoms, and at least one of R ₁ to R ₅ has 9 or more chain- The branch is a straight chain.

In one example, R ₁ to R ₅ R ₁ , R ₂ , R ₄ And R ₅ are each independently hydrogen or an alkyl group having 1 to 8 carbon atoms; Or hydrogen or an alkyl group having 1 to 4 carbon atoms; Or hydrogen, and R < ₃ > may be a straight chain having at least 9 chain-forming atoms.

The term chain forming atom in the present application means an atom forming a straight chain structure of a certain chain. The number of chain-forming atoms is calculated by the number of atoms forming the longest straight chain, and the number of the other atoms bonded to the chain-forming atoms (for example, the chain- A hydrogen atom bonded to the carbon atom in the case of a carbon atom, etc.) is not calculated. In the case of a branched chain, the number of chain forming atoms can be calculated as the number of chain forming atoms forming the longest straight chain. For example, when the side chain is an n-pentyl group, all of the chain-forming atoms are carbon atoms, and the number of the chain-forming atoms is 5 even when the side chain is a 2-methylpentyl group. The chain-forming atom may be exemplified by carbon, oxygen, sulfur or nitrogen, and a suitable chain-forming atom may be carbon, oxygen or nitrogen, or carbon or oxygen. The number of chain-forming atoms may be 8 or more, 9 or more, 10 or more, 11 or more, or 12 or more. The number of the chain-forming atoms may be 30 or less, 25 or less, 20 or less, or 16 or less.

The unit of the formula (1) can make the block copolymer exhibit excellent self-assembling properties.

In one example, the chain may be a straight chain hydrocarbon chain such as a straight chain alkyl group. In this case, the alkyl group may be an alkyl group having 9 or more carbon atoms, 9 to 30 carbon atoms, 9 to 25 carbon atoms, 9 to 20 carbon atoms, or 9 to 16 carbon atoms. At least one of the carbon atoms of the alkyl group may optionally be substituted with an oxygen atom, and at least one hydrogen atom of the alkyl group may be optionally substituted by another substituent.

The straight chain hydrocarbon chain may optionally contain at least one heteroatom. Here, the hetero atom may be an oxygen atom or a nitrogen atom.

The chain may be, for example, an alkyl group, an alkoxy group or an alkoxyalkyl group. In this case, the number of carbon and oxygen atoms in the alkyl group, alkoxy group or alkoxyalkyl group may be 9 or more, 9 to 30, 9 to 25, 9 to 20 or 9 to 16.

The type of another block (hereinafter, referred to as a second block) that can be included in the block copolymer together with the first block is not particularly limited.

For example, the second block may be a polystyrene block such as a polyvinyl pyrrolidone block, a polylactic acid block, a polyvinyl pyridine block, polystyrene or poly trimethylsilyl styrene, A polyolefin block such as a polyalkylene oxide block such as polyethylene oxide, a polyacrylate block, a polybutadiene block, a polyisoprene block or polyethylene is exemplified .

In a suitable example, the second block may be a block represented by the following formula (2).

The block copolymer according to claim 1, further comprising a second block represented by the following formula (2): < EMI ID =

(2)

In Formula (2), R ₁ is hydrogen or an alkyl group, and R ₂ is an alkyl group.

In the formula (2), R ₁ is hydrogen or an alkyl group having 1 to 4 carbon atoms in another example; Hydrogen or a methyl group; Or a methyl group.

In another embodiment, R ₂ in Formula 2 may be 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 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 block of the block copolymer by using a monomer capable of forming a desired block.

For example, the block copolymer can be prepared by the LRP (Living Radical Polymerization) method using the above monomers. For example, anionic polymerization in which an organic rare earth metal complex is used as a polymerization initiator, or an organic alkali metal compound is used as a polymerization initiator in the presence of an inorganic acid salt such as a salt of an alkali metal or an alkaline earth metal, An atomic transfer radical polymerization method (ATRP) using an atom transfer radical polymerization agent as a polymerization initiator, and an atom transfer radical polymerization agent as a polymerization initiator, (ATRP), Initiators for Continuous Activator Regeneration (ATR), Atomic Transfer Radical Polymerization (ATRP), Inorganic Reducing Agent Reversible Additive - Reversible addition-cleavage chain transfer using cleavage chain transfer agent 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 includes polymerizing a reactant containing monomers capable of forming the block in the presence of a radical initiator and a living radical polymerization reagent by living radical polymerization .

The method of forming the other block included in the copolymer together with the block formed by using the monomer in the production of the block copolymer is not particularly limited and may be appropriately selected in consideration of the kind of the desired block, Block can be formed.

The preparation of the block copolymer may further include, for example, a step of precipitating the polymerization product produced through the above process in the non-solvent.

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

The living radical polymerization process can be carried out in the presence of a base such as, for example, methylene chloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, acetone, chloroform, tetrahydrofuran, dioxane, monoglyme, diglyme, Amide, dimethylsulfoxide or dimethylacetamide, and the like.

Examples of the non-solvent include ethers such as alcohols such as methanol, ethanol, n-propanol or isopropanol, glycols such as ethylene glycol, n-hexane, cyclohexane, n-heptane or petroleum ether, But is not limited thereto.

Since the block copolymer contains two or more chains of chains linked by covalent bonds, phase separation occurs. The block copolymer of the present application exhibits excellent phase separation characteristics and can form a nanoscale structure by microphase seperation if necessary. The shape and size of the nanostructure can be controlled by the size (molecular weight, etc.) of the block copolymer, the relative ratio of the blocks, and the like. Examples of the structure formed by phase separation include a spherical shape, a cylinder, a gyroid, a lamellar structure and an inverted structure, and the ability of the block copolymer to form such a structure can be referred to as self-assembling property.

The number average molecular weight (Mn) of the block copolymer may be in the range of, for example, 3,000 to 300,000. In the present specification, the term number average molecular weight refers to a value converted to standard polystyrene measured using GPC (Gel Permeation Chromatograph). In the present specification, the term molecular weight refers to a number average molecular weight unless otherwise specified. 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 other examples. In another example, the molecular weight (Mn) may be 250000 or less, 200000 or less, 1800000 or less, 16000 or less, 1400000 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, Or 25,000 or less. The block copolymer may have a polydispersity (Mw / Mn) in the range of 1.01 to 1.60. In another example, the degree of dispersion may 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 can exhibit proper self-assembling properties. The number average molecular weight of the block copolymer and the like can be adjusted in consideration of the desired self-assembling structure and the like.

When the block copolymer contains at least the first and second blocks, the ratio of the first block of the formula (1) in the block copolymer may be in the range of 10 mol% to 90 mol%.

The present application is also directed to a polymer membrane comprising said block copolymer. The polymer membrane can be used for various purposes, for example, various electronic or electronic devices, a process of forming the pattern, a recording medium such as a magnetic storage medium, a flash memory, or a biosensor.

In one example, the block copolymer in the polymer membrane may be self-assembled to implement a cyclic structure including a sphere, a cylinder, a gyroid or a lamellar, .

For example, within the block of the first or second block or another block covalently bonded thereto, the other segment in the block copolymer may form a regular structure such as a lamellar shape or a cylinder shape.

The present application also relates to a method for forming a polymer film using the block copolymer. The method may include forming a polymer membrane including the block copolymer on a substrate in a self-assembled state. For example, the method may include forming a layer of the block copolymer or a coating liquid in which the block copolymer is diluted with an appropriate solvent on the substrate by applying or the like, and if necessary, aging or heat-treating 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 at, for example, the glass transition temperature or a temperature higher than the phase transition temperature. The time at which this heat treatment is performed is not particularly limited, and can be performed within a range of, for example, about 1 minute to 72 hours, but this can be changed if necessary. The heat treatment temperature of the polymer thin film may be, for example, about 100 ° C to 250 ° C, but may be changed in consideration of the block copolymer to be used.

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

The present application also relates to a method of pattern formation. The above method is a method for selectively removing the first or second block of the block copolymer in a laminate having a substrate and a polymer film formed on the surface of the substrate and self-assembled with the block copolymer . ≪ / RTI > The method may be a method of forming a pattern on the substrate. For example, the method may include forming a polymeric film comprising the block copolymer on a substrate, selectively removing one or more blocks of the block copolymer present in the film, and then etching the substrate . In this way, it is possible to form, for example, a nanoscale fine pattern. In addition, various patterns such as nano-rods, nano-holes, and the like can be formed through the above-described method depending on the type of the block copolymer in the polymer film. If necessary, the block copolymer may be mixed with another copolymer or homopolymer for pattern formation. The type of the substrate to be applied to this method is not particularly limited and may be selected as required. For example, silicon oxide or the like may be applied.

For example, the method can form a nanoscale pattern of silicon oxide that exhibits a high aspect ratio. For example, the polymer film is formed on silicon oxide, and one block of the block copolymer is selectively removed while the block copolymer in the polymer film forms a predetermined structure. Thereafter, the silicon oxide is removed in various ways, for example, , Reactive ion etching, or the like to form various patterns including patterns of nano-rods or nano holes. In addition, it is possible to realize a nano pattern having a large aspect ratio through such a method.

For example, the pattern can be implemented in a scale of several tens of nanometers, and such a pattern can be utilized for various purposes including, for example, a next-generation information electronic magnetic recording medium and the like.

For example, according to the above method, a pattern in which nanostructures having a width of about 3 nm to 40 nm, for example, nanowires are arranged at intervals of about 6 nm to 80 nm, can be formed. In another example, it is possible to implement a structure in which the width is about 3 nm to 40 nm, for example, nanoholes having a diameter of about 6 nm to 80 nm are formed.

Also, in the above structure, the nanowires and nano holes can have a large aspect ratio.

The method of selectively removing one block of the block copolymer in the above method is not particularly limited. For example, a method of removing a relatively soft block by irradiating an appropriate electromagnetic wave, for example, ultraviolet light, Can be used. In this case, the ultraviolet ray irradiation conditions are determined depending on the type of the block of the block copolymer, and can be performed, for example, by irradiating ultraviolet light having a wavelength of about 254 nm for 1 minute to 60 minutes.

In addition, the ultraviolet irradiation may be followed by a step of treating the polymer membrane with an acid or the like to further remove the segment decomposed by ultraviolet rays.

The step of selectively etching the substrate using the polymer film having the removed block as a mask is not particularly limited. For example, the step of etching the substrate may be performed by a reactive ion etching step using CF 4 / Ar ions or the like. A step of removing the polymer membrane from the substrate by an oxygen plasma treatment or the like can also be performed.

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

1 and 2 are AFM images of a polymer membrane.

Hereinafter, the present application will be described in detail by way of examples and comparative examples according to the present application, but the scope of the present application is not limited by the following examples.

One. NMR  Measuring method

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

<Application Abbreviation>

br = broad signal, s = singlet, d = doublet, dd = doublet, t = triplet, dt = double triplet, q = quartet, p = octet, m = polyline.

2. GPC ( Come Permeation Chromatograph )

The number average molecular weight (Mn) and the molecular weight distribution were measured using GPC (Gel Permeation Chromatography). The measurement conditions were as follows.

&Lt; GPC measurement condition >

Devices: 1200 series from Agilent Technologies

Column: Using PLgel mixed B from Polymer laboratories

Solvent: THF

Column temperature: 35 ° C

Sample concentration: 1 mg / mL, 200 L injection

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

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

Manufacturing example  One: money - Of dodecylstyrene (A)  synthesis

The p-dodecylstyrene (A) was synthesized in the following manner. 4-bromostyrene (5.0 g, 27.3 mmol) and magnesium turnings (0.664 g, 27.31 mmol) were placed in a 100 mL flask, and 30 mL of dehydrated tetrahydrofuran (THF) , A small amount of iodine was added as an iodine catalyst, and the mixture was stirred at room temperature for about 6 hours under a nitrogen atmosphere to synthesize a grignard reagent. 1-bromododecane was added to another 100 mL flask, and the prepared Grignard reagent was slowly added at 0 ^° C, followed by dilithium tetrachlorocuprate (II) solution (8.2 mL, 0.82 mmol) After that, the temperature was raised to room temperature and stirred for 3 hours. At the end of the reaction, tetrahydrofuran was removed and the desired compound (2.54 g, 9.32 mmol) was obtained as a liquid through column chromatography using hexane as a mobile phase.

< NMR  Analysis results>

_{^{1 H-NMR (CDCl 3)}} : d7.33 (dd, 2H); d 7.14 (dd, 2 H); [delta] 6.70 (dd, 1H); d5.71 (d, 1 H); d 5.18 (d, 1 H); d 2.59 (t, 2H); d 1.60 (p, 2H); d 1.31-1.26 (m, 18H); d0.89 (t, 3H).

Manufacturing example  2: money - Dodecyloxymethyl styrene (B)

The para-dodecyloxymethylstyrene (B) was synthesized in the following manner. 4-chloromethylstyrene (22.1 g, 144.8 mmol) and 1-dodecanol (30.0 g, 160.1 mmol) were dissolved in 300 mL tetrahydrofuran (THF) And the temperature was lowered to 0 ^° C. Sodium hydride (NaH) (7,7 g, 320.8 mmol) was added in small portions, stirred for 1 hour, heated at 70 ^° C, and reacted for 24 hours. At the end of the reaction, the reaction mixture was cooled to room temperature, and a small amount of water was added to the ice water to react with remaining sodium hydride. After removing the reaction solvent, tetrahydrofuran, the organic layer was collected by extraction with dichloromethane (DCM) / secondary pure water. The resulting compound was purified by column chromatography using hexane / dichloromethane as a mobile phase, To obtain the title compound (23.9 g, 79.0 mmol).

< NMR  Analysis results>

¹ H-NMR (CDCl ₃ ):? 7.39 (dd, 2H); d 7.30 (dd, 2 H); [delta] 6.71 (dd, 1H); d5.74 (d, 1 H); d5.23 (d, 1 H); d4.49 (s, 2H); d3.46 (t, 2H); d 1.61 (p, 2H); d 1.37-1.26 (m, 16H); d0.89 (t, 3H).

Example  One:

A large initiator (number average molecular weight Mn: 7000, molecular weight distribution PDI: 1.16) was synthesized by reacting azobisisobutyronitrile (AIBN) and RAFT (Reversible Addition) chain transfer agent with methyl methacrylate (MMA) . The synthesized macromolecule initiator was dissolved in toluene (solvent: 20 wt.%) With the compound (A) prepared in Preparation Example 1 and AIBN (Azobisisobutyronitrile) in a weight ratio of 1: 70: 0.5 %), Which was reacted in a nitrogen atmosphere at 80 ^° C for 16 hours to prepare a block copolymer. The number average molecular weight of the block copolymer was about 19200 and the molecular weight distribution was 1.17.

Example  2:

Except that a large initiator (number average molecular weight Mn: 8400, molecular weight distribution PDI: 1.15) was synthesized in the same manner as in Example 1 and the compound (B) of Production Example 2 was used instead of the compound (A) A block copolymer was prepared in the same manner as in Example 2. The number average molecular weight of the prepared block copolymer was about 21900 and the molecular weight distribution was 1.19.

Test Example  1. Identification of self-assembly pattern

The coating solution prepared by diluting the block copolymer synthesized in Example 1 or 2 with toluene to a concentration of about 1.0 wt% was coated on a silicon wafer substrate at a speed of 3000 rpm for 60 seconds using a spin coater to form a polymer thin film. The thin films were annealed at 160 ° C for 1 hour to express nanostructures on the surface of the thin films. The expressed nanostructures were measured by AFM (Atomic Force Microscope). Fig. 1 shows results for Example 1, and Fig. 2 shows results for Example 2. Fig.

Claims (14)

1. A block copolymer comprising a first block represented by the following Formula 1:
[Chemical Formula 1]

In formula (1), X ₂ represents a single bond, an oxygen atom, a sulfur atom, a -S (═O) ₂ -alkylene group, an alkenylene group or an alkynylene group, and each of R ₁ to R ₅ independently represents hydrogen, At least one of R ₁ to R ₅ is a straight-chain chain having at least 9 chain-forming atoms.
The block copolymer according to claim 1, wherein X is a single bond or an oxygen atom.
The block copolymer of claim 1, wherein the straight chain comprises from 9 to 20 chain forming atoms. The block copolymer of claim 1, wherein the chain-forming atoms are carbon, oxygen, nitrogen, or sulfur. The block copolymer according to claim 1, wherein the chain-forming atom is carbon or oxygen. The block copolymer according to claim 1, wherein the straight chain is a hydrocarbon chain which may contain at least one hetero atom. The block copolymer according to claim 6, wherein the hetero atom is an oxygen atom. The block copolymer according to claim 1, wherein the straight chain is an alkyl group, an alkoxy group or an alkoxyalkyl group. The block copolymer according to claim 1, further comprising a second block represented by the following formula (2): &lt; EMI ID =
(2)

In Formula (2), R ₁ is hydrogen or an alkyl group, and R ₂ is an alkyl group.
The block copolymer according to claim 9, wherein R ₁ in the general formula (2) is an alkyl group having 1 to 4 carbon atoms.
The block copolymer according to claim 9, wherein R ₂ in the general formula (2) is an alkyl group having 1 to 4 carbon atoms.
A polymer membrane comprising the self-assembled block copolymer of claim 1. A method for forming a polymer membrane, which comprises forming on a substrate a self-assembled polymer membrane comprising the block copolymer of claim 1. A method for selectively removing a first block of a block copolymer or a block different from the first block in a laminate having a substrate and a polymer membrane formed on the substrate and self-assembled with the block copolymer of claim 1 &Lt; / RTI &gt;

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