Monomer and block copolymer

Abstract

The present application relates to monomers, methods for preparing block copolymers, block copolymers and their applications. The monomers may form a block copolymer which has an excellent self assembling property and phase separation and to which various required functions can be freely applied as necessary.

Claims

1. A method for preparing a block copolymer, wherein the block copolymer is prepared by using a monomer represented by Formula 1: ##STR00028## wherein the R is hydrogen or an alkyl group, the X is C(O)X.sub.1 or X.sub.1C(O), where the X.sub.1 is an oxygen atom or a sulfur atom, and the Y is a monovalent substituent represented by Formula 2 below:
PQZ[Formula 2] wherein the P is an arylene group having 6 to 12 carbon atoms, the Q is a single bond, an oxygen atom or NR.sub.3, wherein the R.sub.3 is hydrogen or an alkyl group, and the Z is a chain having 8 or more chain-forming atoms.

2. The method according to claim 1, wherein the R is hydrogen or an alkyl group having 1 to 4 carbon atoms.

3. The method according to claim 1, wherein the X is C(O)O or OC(O).

4. The method according to claim 1, wherein the X is C(O)O.

5. The method according to claim 1, wherein the chain comprises 8 to 20 chain-forming atoms.

6. The method according to claim 1, wherein the chain-forming atom is a carbon, an oxygen, a nitrogen or a sulfur.

7. The method according to claim 1, wherein the chain-forming atom is a carbon or an oxygen.

8. The method according to claim 1, wherein the chain is a linear hydrocarbon chain.

9. The method according to claim 1, wherein the monomer is represented by Formula 3: ##STR00029## wherein the R is hydrogen or an alkyl group having 1 to 4 carbon atom(s), the X is C(O)O, the P is an arylene having 6 to 12 carbon atoms, the Q is an oxygen atom and the Z is a chain having 8 or more chain-forming atoms.

Description

BRIEF DESCRIPTION OF FIGURES

(1) FIGS. 1 to 15 are SEM or AFM images of polymer layers.

(2) FIGS. 16 to 20 show results of GISAXS analysis on polymer layers.

EFFECTS

(3) The present application may provide monomers, methods for preparing block copolymers, block copolymers and their applications. The monomers may form a block copolymer which has an excellent self assembling property and phase separation and to which various required functions can be freely applied as necessary.

ILLUSTRATIVE EMBODIMENTS

(4) Hereinafter, the present application will be described in detail with reference to Examples and Comparative Examples, but the scope of the present application is not limited to the following examples.

(5) 1. NMR Analysis

(6) The NMR analysis was performed at the room temperature by using a NMR spectrometer including a Varian Unity Inova (500 MHz) spectrometer having a triple resonance 5 mm probe. A sample to be analyzed was used after diluting it in solvent (CDCl.sub.3) for the NMR analysis to a concentration of approximately 10 mg/ml and a chemical shift () was expressed in ppm.

(7) <Abbreviation>

(8) br=wide signal, s=singlet, d=doublet, dd=double doublet, t=triplet, dt=double triplet, q=quadruplet, p=quintuplet, m=multiplet

(9) 2. GPC (Gel Permeation Chromatograph)

(10) The number average molecular weight and the polydispersity were measured by the GPC (Gel Permeation Chromatograph). In a 5 mL vial, a block copolymer or a macroinitiator to be measured of Example or Comparative Example and then diluted to a concentration of about 1 mg/mL. Then, the standard sample for a calibration and a sample to be analyzed were filtered by a syringe filter (pore size: 0.45 m) and then analyzed. ChemStation from the Agilent technologies, Co. was used as an analysis program. The number average molecular weight (Mn) and the weight average molecular weight (Mw) were obtained by comparing an elution time of the sample with a calibration curve and then the polydispersity (PDI) was obtained from their ratio (Mw/Mn). The measuring condition of the GPC was as below.

(11) <GPC Measuring Condition>

(12) Device: a 1200 series from Agilent technologies, Co.

(13) Column: two of PLgel mixed B from Polymer laboratories, Co. were used

(14) Solvent: THF

(15) Temperature of the column: 35 C.

(16) Concentration of Sample: 1 mg/mL, 200 L injection

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

Example 1

(18) A compound (DPM-C12) of the Formula A below was synthesized by the below method. To a 250 mL flask, hydroquinone (10.0 g, 94.2 mmole) and 1-bromododecane (23.5 g, 94.2 mmole) were added and dissolved in 100 mL acetonitrile, an excessive amount of potassium carbonate was added thereto and then the mixture was reacted at 75 C. for approximately 48 hours under nitrogen. After the reaction, remaining potassium carbonate and acetonitrile used for the reaction were removed. The work up was performed by adding a mixed solvent of dichloromethane (DCM) and water, and separated organic layers were collected and dehydrated through MgSO.sub.4. Subsequently, a white solid intermediate was obtained with a yield of approximately 37% using DCM through column chromatography.

(19) <NMR Analysis Result of the Intermediate>

(20) .sup.1H-NMR (CDCl.sub.3): 6.77 (dd, 4H); 4.45 (s, 1H); 3.89 (t, 2H); 1.75 (p, 2H); 1.43 (p, 2H); 1.33-1.26 (m, 16H); 0.88 (t, 3H)

(21) The synthesized intermediate (9.8 g, 35.2 mmole), methacrylic acid (6.0 g, 69.7 mmole), dicyclohexylcarbodiimide (DCC; 10.8 g, 52.3 mmole) and p-dimethylaminopyridine (DMPA; 1.7 g, 13.9 mmol) were put into a flask, 120 ml of methylenechloride was added, and a reaction was performed at the room temperature for 24 hours under nitrogen. After the reaction was completed, a urea salt produced in the reaction was removed through a filter, and remaining methylenechloride was also removed. Impurities were removed using hexane and DCM (dichloromethane) as mobile phases though column chromatography, and the obtained product was recrystallized in a mixed solvent of methanol and water (mixed in 1:1 weight ratio), thereby obtaining a white solid product (DPM-C12)(7.7 g, 22.2 mmol) with a yield of 63%.

(22) <NMR Analysis Result with Respect to DPM-C12>

(23) .sup.1H-NMR (CDCl.sub.3): 7.02 (dd, 2H); 6.89 (dd, 2H); 6.32 (dt, 1H); 5.73 (dt, 1H); 3.94 (1, 2H); 2.05 (dd, 3H); 1.76 (p, 2H); 1.43 (p, 2H); 1.34-1.27 (m, 16H); 0.88 (t, 3H)

(24) ##STR00019##

(25) In the above, the R is a linear alkyl having 12 carbon atoms.

Example 2

(26) A compound (DPM-C8) of the Formula B below was synthesized according to the method of Example 1, except that 1-bromooctane was used instead of the 1-bromododecane. The NMR analysis result with respect to the above compound is as below.

(27) <NMR Analysis Result with Respect to DPM-C8>

(28) .sup.1H-NMR (CDCl.sub.3): 7.02 (dd, 2H); 6.89 (dd, 2H); 6.32 (dt, 1H); 5.73 (dt, 1H); 3.94 (t, 2H); 2.05 (dd, 3H); 1.76 (p, 2H); 1.45 (p, 2H); 1.33-1.29 (m, 8H); 0.89 (t, 3H)

(29) ##STR00020##

(30) In the above, the R is a linear alkyl having 8 carbon atoms.

Example 3

(31) A compound (DPM-C10) of the Formula C below was synthesized according to the method of Example 1, except that 1-bromodecane was used instead of the 1-bromododecane. The NMR analysis result with respect to the above compound is as below.

(32) <NMR Analysis Result with Respect to DPM-C10>

(33) .sup.1H-NMR (CDCl.sub.3): 7.02 (dd, 2H); 6.89 (dd, 2H); 6.33 (dt, 1H); 5.72 (dt, 1H); 3.94 (1, 2H); 2.06 (dd, 3H); 1.77 (p, 2H); 1.45 (p, 2H); 1.34-1.28 (m, 12H); 0.89 (1, 3H)

(34) ##STR00021##

(35) In the above, the R is a linear alkyl having 10 carbon atoms.

Example 4

(36) A compound (DPM-C14) of the Formula D below was synthesized according to the method of Example 1, except that 1-bromotetradecane was used instead of the 1-bromododecane. The NMR analysis result with respect to the above compound is as below.

(37) <NMR Analysis Result with Respect to DPM-C14>

(38) .sup.1H-NMR (CDCl.sub.3): 7.02 (dd, 2H); 6.89 (dd, 2H); 6.33 (dt, 1H); 5.73 (dt, 1H); 3.94 (t, 2H); 2.05 (dd, 3H); 1.77 (p, 2H); 1.45 (p, 2H); 1.36-1.27 (m, 20H); 0.88 (t, 3H.)

(39) ##STR00022##

(40) In the above, the R is a linear alkyl having 14 carbon atoms.

Example 5

(41) A compound (DPM-C16) of the Formula E below was synthesized according to the method of Example 1, except that 1-bromohexadecane was used instead of the 1-bromododecane. The NMR analysis result with respect to the above compound is as below.

(42) <NMR analysis result with respect to DPM-C16>

(43) .sup.1H-NMR (CDCl.sub.3): 7.01 (dd, 2H); 6.88 (dd, 2H); 6.32 (dt, 1H); 5.73 (dt, 1H); 3.94 (t, 2H); 2.05 (dd, 3H); 1.77 (p, 2H); 1.45 (p, 2H); 1.36-1.26 (m, 24H); 0.89 (t, 3H)

(44) ##STR00023##

(45) In the above, the R is a linear alkyl having 16 carbon atoms.

Example 6

(46) A compound (DPM-N2) of the Formula F below was synthesized by the below method. To a 500 mL flask, Pd/C (palladium on carbon) (1.13 g, 1.06 mmole) and 200 mL of 2-propanol were added and then ammonium formate dissolved in 20 mL of water was added, and then the Pd/C was activated by performing a reaction at the room temperature for 1 minute. Then, 4-aminophenol (1.15 g, 10.6 mmole) and lauric aldehyde (1.95 g, 10.6 mmole) were added thereto and the mixture was reacted at the room temperature for 1 minute by stirring it under nitrogen. After the reaction, the Pd/C was removed and the 2-propanol used for the reaction was removed, and then the mixture was extracted by water and methylene chloride so as to remove unreacted products. An organic layer was collected and dehydrated through MgSO.sub.4. A crude product was purified by a column chromatography (mobile phase: hexane/ethyl acetate) and thereby a colorless solid intermediate (1.98 g, 7.1 mmole) was obtained (yield: 67 weight %).

(47) <NMR Analysis Result of the Intermediate>

(48) .sup.1H-NMR (DMSO-d): 6.69 (dd, 2H); 6.53 (dd, 2H); 3.05 (t, 2H); 1.59 (p, 2H); 1.40-1.26 (m, 16H); 0.88 (t, 3H)

(49) The synthesized intermediate (1.98 g, 7.1 mmole), methacrylic acid (0.92 g, 10.7 mmole), dicyclohexylcarbodiimide (DCC; 2.21 g, 10.7 mmole) and p-dimethylaminopyridine (DMPA; 0.35 g, 2.8 mmol) were put into a flask, 100 ml of methylenechloride was added, and a reaction was performed at the room temperature for 24 hours under nitrogen. After the reaction was completed, a urea salt produced during the reaction was removed through a filter, and remaining methylenechloride was also removed. Impurities were removed using hexane and DCM (dichloromethane) as mobile phases though column chromatography, and the obtained product was recrystallized in a mixed solvent (methanol:water=3:1 (weight ratio)) of methanol and water, thereby obtaining a white solid product (DPM-N2)(1.94 g, 5.6 mmole) with a yield of 79%.

(50) <NMR Analysis Result with Respect to DPM-N2>

(51) .sup.1H-NMR (CDCl.sub.3): 6.92 (dd, 2H); 6.58 (dd, 2H); 6.31 (dt, 1H); 5.70 (dt, 1H); 3.60 (s, 1H); 3.08 (t, 2H); 2.05 (dd, 3H); 1.61 (p, 2H); 1.30-1.27 (m, 16H); 0.88 (t, 3H)

(52) ##STR00024##

(53) In the above, the R is a linear alkyl having 12 carbon atoms.

Comparative Example 1

(54) A compound (DPM-C4) of the Formula G below was synthesized according to the method of Example 1, except that 1-bromobutane was used instead of the 1-bromododecane. The NMR analysis result with respect to the above compound is as below.

(55) <NMR Analysis Result with Respect to DPM-C4>

(56) .sup.1H-NMR (CDCl.sub.3): 7.02 (dd, 2H); 6.89 (dd, 2H); 6.33 (dt, 1H); 5.73 (dt, 1H); 3.95 (t, 2H); 2.06 (dd, 3H); 1.76 (p, 2H); 1.49 (p, 2H); 0.98 (t, 3H)

(57) ##STR00025##

(58) In the above, the R is a linear alkyl having 4 carbon atoms.

Example 7

(59) 2.0 g of the compound (DPM-C12) of Example 1, 64 mg of RAFT (Reversible Addition-Fragmentation chain transfer) reagent (cyanoisopropyl dithiobenzoate), 23 mg of AIBN (azobisisobutyronitrile) and 5.34 mL of benzene were added to a 10 mL flask and then were stirred at the room temperature for 30 minutes and then the RAFT (reversible addition fragmentation chain transfer) polymerization was performed at 70 C. for 4 hours. After the polymerization, the reacted solution was precipitated in 250 mL of methanol that was an extraction solvent, was vacuum filtered and dried so as to obtain pink macroinitiator. The yield of the macroinitiator was about 86%, and its number average molecular weight (Mn) and polydispersity (Mw/Mn) were 9,000 and 1.16, respectively.

(60) 0.3 g of the macroinitiator, 2.7174 g of pentafluorostyrene and 1.306 mL of benzene were added to a 10 mL Schlenk flask and then were stirred at the room temperature for 30 minutes and then the RAFT (reversible addition fragmentation chain transfer) polymerization was performed at 115 C. for 4 hours. After the polymerization, the reacted solution was precipitated in 250 mL of methanol that was an extraction solvent, was vacuum filtered and dried so as to obtain light pink block copolymer. The yield of the block copolymer was about 18%, and its number average molecular weight (Mn) and polydispersity (Mw/Mn) were 16,300 and 1.13, respectively. The block copolymer includes the first block derived from the compound (DPM-C12) of Example 1 and the second block derived from the pentafluorostyrene.

Example 8

(61) A block copolymer was prepared by the same method as in Example 7 except that a macroinitiator prepared by using the compound (DPM-C8) of Example 2 instead of the compound (DPM-C12) of Example 1 and pentafluorostyrene were used. The block copolymer includes the first block derived from the compound (DPM-C8) of Example 2 and the second block derived from the pentafluorostyrene.

Example 9

(62) A block copolymer was prepared by the same method as in Example 7 except that a macroinitiator prepared by using the compound (DPM-C10) of Example 3 instead of the compound (DPM-C12) of Example 1 and pentafluorostyrene were used. The block copolymer includes the first block derived from the compound (DPM-C10) of Example 3 and the second block derived from the pentafluorostyrene.

Example 10

(63) A block copolymer was prepared by the same method as in Example 7 except that a macroinitiator prepared by using the compound (DPM-C14) of Example 4 instead of the compound (DPM-C12) of Example 1 and pentafluorostyrene were used. The block copolymer includes the first block derived from the compound (DPM-C14) of Example 4 and the second block derived from the pentafluorostyrene.

Example 11

(64) A block copolymer was prepared by the same method as in Example 7 except that a macroinitiator prepared by using the compound (DPM-C16) of Example 5 instead of the compound (DPM-C12) of Example 1 and pentafluorostyrene were used. The block copolymer includes the first block derived from the compound (DPM-C16) of Example 5 and the second block derived from the pentafluorostyrene.

Example 12

Synthesis of a Monomer

(65) 3-Hydroxy-1,2,4,5-tetrafluorostyrene was synthesized according to the below method. Pentafluorostyrene (25 g, 129 mmole) was added to a mixed solution of 400 mL of tert-butanol and potassium hydroxide (37.5 g, 161 mmole); and then was subjected to a reflux reaction for 2 hours. The product after the reaction was cooled to the room temperature, 1200 mL of water was added and the remaining butanol used for the reaction was volatilized. The adduct was extracted 3 times by diethyl ether (300 mL), an aqueous layer was acidified by 10 weight % of hydrochloric acid solution until its pH became 3, and thereby target product was precipitated. Precipitated product was extracted 3 times by diethyl ether (300 mL) and an organic layer was collected. The organic layer was dehydrated by MgSO.sub.4 and solvent was removed. Crude product was purified in a column chromatograph by using hexane and DCM (dichloromethane) as mobile phase and thereby colorless liquid 3-hydroxy-1,2,4,5-tetrafluorostyrene (11.4 g) was obtained. Its NMR analysis result is as below.

(66) <NMR Analysis Result>

(67) .sup.1H-NMR (DMSO-d): 11.7 (s, 1H); 6.60 (dd, 1H); 5.89 (d, 1H); 5.62 (d, 1H)

(68) Synthesis of a Block Copolymer

(69) In benzene, AIBN (azobisisobutyronitrile), RAFT (reversible addition fragmentation chain transfer) reagent (2-cyano-2-propyl dodecyl trithiocarbonate) and the compound (DPM-C12) of Example 1 were dissolved in a weight ratio of 50:1:0.2 (DPM-C12:RAFT reagent:AIBN) (Concentration: 70 weight %), and then a macroinitiator (a number average molecular weight: 14000, polydispersity: 1.2) was prepared by reacting the mixture for 4 hours at 70 C. under nitrogen. Then, in benzene, the synthesized macroinitiator, 3-hydroxy-1,2,4,5-tetrafluorostyrene (TFS-OH) and AIBN (azobisisobutyronitrile) were dissolved in a weight ratio of 1:200:0.5 (the macroinitiator:TFS-OH:AIBN) (Concentration: 30 weight %), and then a block copolymer (a number average molecular weight: 35000, polydispersity: 1.2) was prepared by reacting the mixture for 6 hours at 70 C. under nitrogen. The block copolymer includes the first block derived from the compound of Example 1 and the second block derived from the 3-hydroxy-1,2,4,5-tetrafluorostyrene.

Example 13

Synthesis of a Monomer

(70) The compound of the Formula H below was synthesized according to the below method. Phthalimide (10.0 g, 54 mmole) and chloromethylstyrene (8.2 g, 54 mmole) were added to 50 mL of DMF (dimethyl formamide) and then were reacted for 18 hours at 55 C. under nitrogen. After the reaction, 100 mL of ethyl acetate and 100 mL of distilled water were added to the reacted product, and then an organic layer was collected and then washed by brine solution. Collected organic layer was treated by MgSO.sub.4 and thereby water was removed and then solvent was finally removed and then re-crystallized by pentane so as to obtain white solid target compound (11.1 g). Its NMR analysis result is as below.

(71) <NMR Analysis Result>

(72) .sup.1H-NMR (CDCl.sub.3): 7.84 (dd, 2H); 87.70 (dd, 2H); 7.40-7.34 (m, 4H); 6.67 (dd, 1H); 5.71 (d, 1H); 5.22 (d, 1H); 4.83 (s, 2H)

(73) ##STR00026##

(74) Synthesis of a Block Copolymer

(75) In benzene, AIBN (azobisisobutyronitrile), RAFT (reversible addition fragmentation chain transfer) reagent (2-cyano-2-propyl dodecyl trithiocarbonate) and the compound (DPM-C12) of Example 1 were dissolved in a weight ratio of 50:1:0.2 (DPM-C12:RAFT reagent:AIBN) (Concentration: 70 weight %), and then a macroinitiator (a number average molecular weight: 14000, polydispersity: 1.2) was prepared by reacting the mixture for 4 hours at 70 C. under nitrogen. Then, in benzene, the synthesized macroinitiator, the compound (TFS-PhIM) of Formula H and AIBN (azobisisobutyronitrile) were dissolved in a weight ratio of 1:200:0.5 (the macroinitiator:TFS-PhIM:AIBN) (Concentration: 30 weight %), and then a block copolymer (a number average molecular weight: 35000, polydispersity: 1.2) was prepared by reacting the mixture for 6 hours at 70 C. under nitrogen. The block copolymer includes the first block derived from the compound of Example 1 and the second block derived from the compound of Formula H.

Example 14

(76) 0.8662 g of the compound (DPM-C12) of Example 1, 0.5 g of macroinitiator (Macro-PEO)(poly(ethylene glycol)-4-cyano-4-(phenylcarbonothioylthio)pentanoate, a weight average molecular weight: 10,000, sigma aldrich) both end portions of which RAFT (reversible addition fragmentation chain transfer) reagents were linked, 4.1 mg of AIBN (azobisisobutyronitrile) and 3.9 mL of anisole were added to 10 mL Schlenk flask, and then stirred at the room temperature for 30 minutes under nitrogen, and then RAFT (reversible addition fragmentation chain transfer) polymerization was performed in a silicone oil container (70 C.) for 12 hours. After the polymerization, the reacted solution was precipitated in 250 mL of methanol that was an extraction solvent, vacuum filtered and dried so as to synthesize light pink novel block copolymer (a number average molecular weight (Mn): 34300, a polydispersity (Mw/Mn): 1.60). The block copolymer includes the first block derived from the compound of Example 1 and the second block of poly(ethylene oxide) block.

Example 15

(77) 2.0 g of the compound (DPM-C12) of Example 1, 25.5 mg of RAFT (reversible addition fragmentation chain transfer) reagent (cyanoisopropyl dithiobenzoate), 9.4 mg of AIBN (azibisisobutyronitrile) and 5.34 mL of benzene were added to 10 mL Schlenk flask and stirred for 30 minutes at the room temperature and then a RAFT (reversible addition fragmentation chain transfer) polymerization was performed for 4 hours in a silicone oil container (70 C.). After the polymerization, the reacted solution was precipitated in 250 mL of methanol that was an extraction solvent, vacuum filtered and dried so as to synthesize pink macroinitiator both end portions of which RAFT (reversible addition fragmentation chain transfer) reagents were linked to. The yield, a number average molecular weight (Mn) and a polydispersity (Mw/Mn) were 81.6 weight %, 15400 and 1.16, respectively. 1.177 g of styrene, 0.3 g of the above macroinitiator and 0.449 mL of benzene were added to 10 mL Schlenk flask and stirred for 30 minutes at the room temperature and then a RAFT (reversible addition fragmentation chain transfer) polymerization was performed for 4 hours in a silicone oil container (115 C.). After the polymerization, the reacted solution was precipitated in 250 mL of methanol that was an extraction solvent, vacuum filtered and dried so as to synthesize light pink novel block copolymer. The yield, a number average molecular weight (Mn) and a polydispersity (Mw/Mn) were 39.3 weight %, 31800 and 1.25, respectively. The block copolymer includes the first block derived from the compound of Example 1 and the polystyrene block (the second block).

Example 16

(78) 0.33 g of the macroinitiator synthesized in Example 15, 1.889 g of 4-trimethylsilylstyrene, 2.3 mg of AIBN (azobisisobutyronitrile) and 6.484 mL of benzene were added to 10 mL Schlenk flask, and then stirred at the room temperature for 30 minutes under nitrogen, and then RAFT (reversible addition fragmentation chain transfer) polymerization was performed in a silicone oil container (70 C.) for 24 hours. After the polymerization, the reacted solution was precipitated in 250 mL of methanol that was an extraction solvent, vacuum filtered and dried so as to synthesize light pink novel block copolymer. The yield, a number average molecular weight (Mn) and a polydispersity (Mw/Mn) of the block copolymer were 44.2 weight %, 29600 and 1.35, respectively. The block copolymer includes the first block derived from the compound of Example 1 and the poly(4-trimethylsilylstyrene) block (the second block).

Example 18

Synthesis of a Monomer

(79) The compound of the Formula I below was synthesized according to the below method. Pentafluorostyrene (25 g, 129 mmole) was added to a mixed solution of 400 mL of tert-butanol and potassium hydroxide (37.5 g, 161 mmole); and then was subjected to a reflux reaction for 2 hours. The product after the reaction was cooled to the room temperature, 1200 mL of water was added and the remaining butanol used for the reaction was volatilized. The adduct was extracted 3 times by diethyl ether (300 mL), an aqueous layer was acidified by 10 weight % of hydrochloric acid solution until its pH became 3, and thereby target product was precipitated. Precipitated product was extracted 3 times by diethyl ether (300 mL) and an organic layer was collected. The organic layer was dehydrated by MgSO.sub.4 and solvent was removed. Crude product was purified in a column chromatograph by using hexane and DCM (dichloromethane) as mobile phase and thereby a colorless liquid intermediate (3-hydroxy-1,2,4,5-tetrafluorostyrene) (11.4 g) was obtained. Its NMR analysis result is as below.

(80) <NMR Analysis Result>

(81) .sup.1H-NMR (DMSO-d): 11.7 (s, 1H); 6.60 (dd, 1H); 5.89 (d, 1H); 5.62 (d, 1H)

(82) The intermediate (11.4 g, 59 mmole) was dissolved in DCM (dichloromethane) (250 mL) and then imidazole (8.0 g, 118 mmole), DMPA (p-dimethylaminopyridine (0.29 g, 2.4 mmole) and tert-butylchlorodimethylsilane (17.8 g, 118 mmole) were added thereto. The mixture was reacted by stirring it at the room temperature for 24 hours and the reaction was terminated by adding 100 mL of brine and then additional extraction was performed by DCM. A collected organic layer of DCM was dehydrated by MgSO.sub.4 and solvent was removed so as to obtain crude product. Colorless liquid target product (10.5 g) was obtained after purification in a column chromatograph by using hexane and DCM as mobile phase. NMR result of the target product is as below.

(83) <NMR Analysis Result>

(84) .sup.1H-NMR (CDCl.sub.3): 6.62 (dd, 1H); 6.01 (d, 1H); 5.59 (d, 1H); 1.02 (1, 9H), 0.23 (t, 6H)

(85) ##STR00027##

(86) Synthesis of a Block Copolymer

(87) In benzene, AIBN (azobisisobutyronitrile), RAFT (reversible addition fragmentation chain transfer) reagent (2-cyano-2-propyl dodecyl trithiocarbonate) and the compound (DPM-C12) of Example 1 were dissolved in a weight ratio of 50:1:0.2 (DPM-C12:RAFT reagent:AIBN) (Concentration: 70 weight %), and then a macroinitiator (a number average molecular weight: 14000, polydispersity: 1.2) was prepared by reacting the mixture for 4 hours at 70 C. under nitrogen. Then, in benzene, the synthesized macroinitiator, the compound (TFS-S) of Formula I and AIBN (azobisisobutyronitrile) were dissolved in a weight ratio of 1:200:0.5 (the macroinitiator:TFS-S:AIBN) (Concentration: 30 weight %), and then a block copolymer (a number average molecular weight: 35000, polydispersity: 1.2) was prepared by reacting the mixture for 6 hours at 70 C. under nitrogen. The block copolymer includes the first block derived from the compound of Example 1 and the second block derived from the compound of Formula I.

Example 18

(88) In benzene, AIBN (azobisisobutyronitrile), RAFT (reversible addition fragmentation chain transfer) reagent (2-cyano-2-propyl dodecyl trithiocarbonate) and the compound (DPM-N1) of Example 6 were dissolved in a weight ratio of 26:1:0.5 (DPM-C12:RAFT reagent:AIBN) (Concentration: 70 weight %), and then a macroinitiator (a number average molecular weight: 9700, polydispersity: 1.2) was prepared by reacting the mixture for 4 hours at 70 C. under nitrogen. Then, in benzene, the synthesized macroinitiator, pentafluorostyrene (PFS) and AIBN (azobisisobutyronitrile) were dissolved in a weight ratio of 1:600:0.5 (the macroinitiator:PFS:AIBN) (Concentration: 30 weight %), and then a block copolymer (a number average molecular weight: 17300, polydispersity: 1.2) was prepared by reacting the mixture for 6 hours at 115 C. under nitrogen. The block copolymer includes the first block derived from the compound of Example 6 and the second block derived from the pentafluorostyrene.

Comparative Example 2

(89) A block copolymer was prepared by the same method as in Example 7 except that a macroinitiator prepared by using the compound (DPM-C4) of Comparative Example 1 instead of the compound (DPM-C12) of Example 1 and pentafluorostyrene were used. The block copolymer includes the first block derived from the compound (DPM-C4) of Comparative Example 1 and the second block derived from the pentafluorostyrene.

Comparative Example 3

(90) A block copolymer was prepared by the same method as in Example 7 except that a macroinitiator prepared by using 4-methoxyphenyl methacrylate instead of the compound (DPM-C12) of Example 1 and pentafluorostyrene were used. The block copolymer includes the first block derived from the 4-methoxyphenyl methacrylate and the second block derived from the pentafluorostyrene.

Comparative Example 4

(91) A block copolymer was prepared by the same method as in Example 7 except that a macroinitiator prepared by using dodecyl methacrylate instead of the compound (DPM-C12) of Example 1 and pentafluorostyrene were used. The block copolymer includes the first block derived from the dodecyl methacrylate and the second block derived from the pentafluorostyrene.

Test Example 1

(92) Self assembled polymer layers were prepared by using block copolymers of Examples 7 to 18 and Comparative Examples 2 to 4 and the results were observed. Specifically, each block copolymer was dissolved in solvent to a concentration of 1.0 weight % and then was spin-coated on a silicone wafer for 60 seconds by a speed of 3000 rpm. Then, self assembling was performed by a solvent annealing or a thermal annealing. The used solvents and aging methods were stated in the Table 1 below. Then, the self assembling properties were evaluated by subjecting each polymer layer to a SEM (scanning electron microscope) or AFM (atomic force microscopy) analysis. FIGS. 1 to 12 are results of Examples 7 to 18, respectively, and FIGS. 13 to 15 are results of Comparative Examples 2 to 4, respectively.

(93) TABLE-US-00001 TABLE 1 The coating solution The concen- tration of Annealing The used the block Annealing solvent copolymer Annealing method condition Ex. 7 Toluene 1.0 weight % Thermal Annealing 160 C., 1 hour Ex. 8 Toluene 1.0 weight % Thermal Annealing 160 C., 1 hour Ex. 9 Toluene 1.0 weight % Thermal Annealing 160 C., 1 hour Ex. 10 Toluene 1.0 weight % Thermal Annealing 160 C., 1 hour Ex. 11 Toluene 1.0 weight % Thermal Annealing 160 C., 1 hour Ex. 12 Toluene 1.0 weight % Solvent annealing 2 hours Ex. 13 Dioxin 1.0 weight % Solvent annealing 1 hour Ex. 14 Toluene 1.0 weight % Solvent annealing 2 hours Ex. 15 Toluene 1.0 weight % Thermal Annealing 160 C., 1 hour Ex. 16 Toluene 1.0 weight % Solvent annealing 2 hours Ex. 17 Toluene 1.0 weight % Thermal Annealing 160 C., 1 hour Ex. 18 Toluene 1.0 weight % Thermal Annealing 200 C., 1 hour Com. Toluene 1.0 weight % Thermal Annealing 160 C., 1 hour Ex. 2 Com. Toluene 1.0 weight % Thermal Annealing 160 C., 1 hour Ex. 3 Com. Toluene 1.0 weight % Thermal Annealing 160 C., 1 hour Ex. 4 The solvent used in the solvent annealing of Example 12: the mixed solvent of THF (Tetrahydrofuran) and water (THF:water = 4:6 (weight ratio)) The solvent used in the solvent annealing of Example 13: chloroform The solvent used in the solvent annealing of Example 14: the mixed solvent of THF (Tetrahydrofuran) and water (THF:water = 4:6 (weight ratio)) The solvent used in the solvent annealing of Example 16: cyclohexane

Test Example 2

(94) From the Test Example 1, it can be confirmed that the block copolymers in Examples have excellent self assembling properties fundamentally. Among Examples, GISAXS (Grazing Incident Small Angle X ray Scattering) properties were evaluated with respect to the block copolymer prepared in Example 7. The above property was evaluated in a 3C beam line of the Pohang Light Source. The polymer layer was formed by spin-coating a coating solution, which was prepared by dissolving the block copolymer of Example 7 in fluorobenzene so as for a solid content to be 0.7 weight %, on a substrate having a hydrophilic or hydrophobic surface so as for the coated layer to have a thickness of 5 nm (coated area: width=1.5 cm, length=1.5 cm) and drying it for about 1 hour at the room temperature and then subjecting it to the thermal annealing at about 160 C. for about 1 hour. The formed polymer layer was irradiated with X ray so as for an incident angle to be from about 0.12 degrees to 0.23 degrees, which corresponded to an angle between a critical angle of the layer and a critical angle of the substrate, and then the X ray diffraction pattern scattered from the layer was obtained by using a 2D marCCD. At this time, a distance from the layer to the detector was selected so as for the self assembled pattern in the layer to be effectively observed within a range from about 2 m to 3 m. As the substrate having the hydrophilic surface, the substrate having a wetting angle of about 5 degrees with respect to purified water at the room temperature was used, and, as the substrate having the hydrophobic surface, the substrate having a wetting angle of about 60 degrees with respect to purified water at the room temperature was used. FIG. 16 is the result of the GISAXS (Grazing Incident Small Angle X ray Scattering) analysis with respect to the surface having the wetting angle of about 5 degrees with respect to purified water at the room temperature according to the above method. FIG. 17 is the result of the GISAXS (Grazing Incident Small Angle X ray Scattering) analysis with respect to the surface, as the hydrophobic surface, having the wetting angle of about 60 degrees with respect to purified water at the room temperature according to the above method. From the Figures, it can be confirmed that the in-plane phase diffraction patterns are confirmed in any case, and the block copolymer of Example 7 has the vertical aligning property.

(95) Further, block copolymers having different volume fractions were prepared according to the same method as in Example 7, except that the molar ratios of the monomers and the macroinitiators were controlled.

(96) The volume fractions are as below.

(97) TABLE-US-00002 TABLE 2 Volume fraction of Volume fraction of the first block the second block Sample 1 0.7 0.3 Sample 2 0.59 0.41 Sample 3 0.48 0.52

(98) The volume fraction of each block of the block copolymer was calculated based on a molecular weight measured by a GPC (Gel Permeation Chromatogrph) and the density at the room temperature. In the above, the density was measured by the buoyancy method, specifically, was calculated by a mass in solvent (ethanol), of which a mass and a density in the air are known, and the GPC was performed according to the above described method. The results of the GISAXS analysis with respect to the each sample are illustrated in FIGS. 18 to 20. FIGS. 18 to 20 are results with respect to the samples 1 to 3, respectively, and from the figures, it can be confirmed that the in-plane phase diffraction patterns on GISAXS are observed, and therefrom it can be predicted to have the vertical aligning property.

Test Example 3

(99) From the Test Example 1, it can be confirmed that the block copolymers in Examples have excellent self assembling properties fundamentally. Among Examples, surface energies and densities were evaluated with respect to Comparative Examples 2 and 3 and Examples 7 to 11, in which appropriate results were observed.

(100) The surface energy was measured by using the drop shape analyzer (DSA 100 product from KRUSS, Co.). The surface energy was evaluated with respect to the polymer layer formed by spin-coating a coating solution, which was prepared by dissolving the material to be evaluated in fluorobenzene so as for a solid content to be 2 weight %, on a silicone wafer so as for the coated layer to have a thickness of 50 nm (coated area: width=2 cm, length=2 cm) and drying it for about 1 hour at the room temperature and then subjecting it to the thermal annealing at about 160 C. for about 1 hour. The surface energy was calculated from average values which were calculated from average values measured by dropping deionized water (H.sub.2O) and diiodomethane, both of which are liquids of which surface tensions are known, 5 times respectively. In the below Table, the surface energy of each block is the surface energy measured with respect to a homopolymer formed by monomers forming the corresponding block according to the above method.

(101) The method for measuring the density was the same as described above.

(102) The measured results are stated in the below Table.

(103) TABLE-US-00003 TABLE 3 Exs. Com. Exs. 8 9 10 11 12 2 3 The SE 30.83 31.46 27.38 26.924 27.79 37.37 48.95 first De 1 1.04 1.02 0.99 1.00 1.11 1.19 Block VF 0.66 0.57 0.60 0.61 0.61 0.73 0.69 The SE 24.4 24.4 24.4 24.4 24.4 24.4 24.4 Second De 1.57 1.57 1.57 1.57 1.57 1.57 1.57 Block VF 0.34 0.43 0.40 0.39 0.39 0.27 0.31 Difference 6.43 7.06 2.98 2.524 3.39 12.98 24.55 of SE Difference 0.57 0.53 0.55 0.58 0.57 0.46 0.38 of De SE: surface energy (unit: mN/m) De: density (unit: g/cm3) VF: volume fraction Difference of SE: the absolute value of the difference between the surface energies of the first and the second block Difference of De: the absolute value of the difference between the densities of the first and the second block Chain-forming atoms: the number of the chain-forming atoms in the first block Interval: interval (unit: nm) between the first blocks in the self assembled block copolymer n/D: the number of the chain-forming atoms in the first block/Interval between the first blocks in the self assembled block copolymer Ref.: Polystyrene-polymethylmethacrylate block copolymer (the first block: polystyrene block, the second block: polymethylmethacrylate block)

(104) From the above table, it can be confirmed that there are specific tendencies in the cases (Examples 7 to 11) where the appropriate self assembling properties are confirmed. Specifically, in the block copolymers of Examples 7 to 11, the absolute values of differences between surface energies of the first and second blocks are within a range from 2.5 mN/m to 7 mN/m; however Comparative Examples show the absolute values of difference between the surface energies that do not fall within the above range. Further, the first block shows a higher surface energy than the second block, and the range are from 20 mN/m to 35 mN/m. Further, the absolute values of differences between densities of the first and second blocks of the block copolymers of Examples 7 to 11 are 0.3 g/cm.sup.3 or more.

Test Example 4

(105) The result of the XRD analysis with respect to Comparative Examples 2 and 3 and Examples 7 to 11, in which appropriate results were observed, is illustrated in the below Table 4.

(106) TABLE-US-00004 TABLE 4 Exs. Com. Exs. 8 9 10 11 12 2 3 Scattering 1.96 2.41 2.15 1.83 1.72 4.42 3.18 vector (the q value) (unit: nm.sup.1) FWHM 0.57 0.72 0.63 0.45 0.53 0.97 1.06 (unit: nm.sup.1)

(107) The XRD pattern was evaluated by measuring the scattering intensity according to the scattering vector (q) by passing X ray through a sample in a 3C beam line of the Pohang Light Source. As the sample, powder obtained from the block copolymer to which any specific pre-treatment was not performed by purifying it so as to remove impurities therefrom was used after putting it in a cell for measurement of the XRD. During the XRD pattern analysis, as the X ray, X ray, a vertical size of which is 0.023 mm and a horizontal size of which is 0.3 mm was used and, as the detector, the measuring device (for example, 2D marCCD) was used. A 2D diffraction pattern scattered from the sample was obtained as an image, the obtained diffraction pattern was calibrated to the scattering vector (q) by using a silver behenate and then is circular averaged and then plotted as the scattering intensity according to the scattering vector (q). The position and the FWHM of the peak was obtained by plotting the scattering intensity according to the scattering vector (q) and peak fitting. From the above result, it can be confirmed the block copolymers showing excellent self assembling properties show specific XRD patterns, compared to Comparative Examples in which self assembling properties were not confirmed. Specifically, peaks of which the FWHMs is within a range from 0.2 nm.sup.1 to 1.5 nm.sup.1 are observed within a scattering vector's range from 0.5 nm.sup.1 to 10 nm.sup.1; however such peaks are not observed in Comparative Examples.