KR100922182B1 - Amphiphilic Norbornene-based Diblock Copolymers Containing Polyhedral Oligomeric Silsesquioxane Prepared By Living Ring Opening Metathesis Polymerization, And Method For The Preparation Thereof - Google Patents

Abstract

The present invention relates to an amphipathic organic / inorganic block copolymer comprising a hydrophobic polyhedral oligomeric silsesquioxane (POSS) segment and a method for preparing the same, which includes RuCl ₂ (= CHPh) (PCy ₃ ). _{) 2 / CH 2 Cl 2/} 20 ℃ 2- endo-3-exo-5-using system norbornene dicarboxylic acid (2-endo-3-exo -5-Norborene dicarboxylic acid, NBECOOH) and 2- Endo-3-exo-5-norbornene-2,3-dicarboxylic acid bis (trimethylsilyl) ester (2-endo-3-exo-5-Norbornene-2,3-dicarboxylic acid bis (trimethylsilyl) ester, by using the addition reaction of the living ring-opening metathesis polymerization, and subsequently the monomer NBEPOSS NBETMS), poly (NBETMS- -NBEPOSS b) continuously by hydrolysis of the trimethylsilyl group in the copolymer poly (NBECOOH- -NBEPOSS b) copolymer It characterized in that the manufacturing.

Polyhedral oligomeric silsesquioxane, ring-opening metathesis polymerization, block copolymer living polymerization, sequential (continuous) monomer addition

Description

Amphiphilic Norbornene-based Diblock Copolymers Containing Polyhedral Oligomeric Silsesquioxane Prepared By Living Ring Opening Metathesis Polymerization, And Method For The Preparation Thereof}

The present invention relates to an amphipathic norbornene-based block copolymer using living ring-opening metathesis polymerization and a method for preparing the same.

The goal of polymer science is to design and synthesize new polymer materials with custom properties, which is made possible by the development of macromolecular engineering to control molecular weight, molecular weight distribution and molecular design [P. Rempp, E. Franta, and JE Herz, Adv . Polym . Sci . , 88 , 145 (1988); JP Kennedy and B. Ivan, Designed Polymers by Carbocationic Macromolecular Engineering , Hanser, Germany, 1991; K. Hatada, T. Kitayama, and O. Vogl, Eds., Macromolecular Design of Polymeric Materials , Marcel Dekker, New York, 1996; Y. Kwon and R. Faust, Adv . Polym . Sci . , 167 , 107 (2004)]. As a prerequisite for obtaining a block copolymer capable of controlling molecular weight, molecular weight distribution and molecular design as described above, a living polymerization system is used, and living polymerization is the most important method in macromolecular engineering.

Living polymerization such as anion, cation, ring-opening polymerization method, including radicals that have been studied in recent years, can control the degree of polymerization according to reaction time, control the molecular weight, and make the molecular weight distribution uniform. In addition, living polymerization does not disappear by the stop or transfer reaction of the growth center, and it is convenient to attach a functional group to the end of the chain. As an important method for synthesizing, nanostructures between polymers with different components can be controlled and synthesized as designed, and thus a lot of research is being conducted as a method for preparing urea materials for use in nanotechnology.

대 전환 플롯)으로부터 증명된다. 제1차 동역학적 플롯의 직선성은 성장 센터(즉, 종결이 존재하지 않음)의 일정한 농도를 나타낸다. 또한 분자량 대 전환 플롯의 직선성은 전체 중합 반응 동안에 연쇄이동이 존재하지 않음을 입증한다.Living polymerization is characterized by the absence of termination ( K _t = 0) and chain trasfer ( K _tr = 0), so that various polymers and block copolymers are usually produced by living polymerization. In general, the absence of chain transfer and termination results in a linear first order kinetic plot (ln ([M ₀ ] / [M]) versus time) and linear dependence of molecular weight on monomer conversion. dependence of molecular weight on monomer conversion)

Vs. conversion plot). The linearity of the first kinematic plot represents a constant concentration of growth centers (ie no termination). The linearity of the molecular weight versus conversion plot also demonstrates that there is no chain transfer during the entire polymerization reaction.

The first living anionic polymerization was reported in the 1950s [M. Szwarc, Nature , 178 , 1168 (1956)], living polymerizations include group transfer polymerization (GTP), carbocationic polymerization, ring opening metathesis polymerization (ROMP) and atom transfer radical polymerization (atom transfer radical polymerization, ATRP), etc., and has become particularly important and convenient way, as the ROMP catalyst which can maintain the water / functional group occurrence living ROMP can produce a block copolymer [KJ Ivin and CJ Mol, Olefin Metathesis and Metathesis Polymerization , Academic Press, London (1997); RH Grubbs, Tetrahedron , 60 , 7117 (2004); RR Shrock and AH Hoveyda, Angewandte Chemie International Edition , 42 , 4592 (2003); CW Bielawski and RH Grubbs, Prog . Polym . Sci . , 32 , 1 (2007)].

As monomers for carrying out the ROMP, strained cycloalkenes, norborene derivatives, etc., in which strained rings can easily react with a ROMP catalyst, are known. Based on the monomers, various homopolymers and block copolymers are synthesized by living polymerization.

Recently, organic / inorganic hybrid nanocomposites containing block copolymers having nanoparticles (eg, polyhedral oligomeric silsesquioxanes (POSS)) covalently attached to one polymer block have been of considerable interest. And the nanocomposites have a highly ordered morphological complexity of a length scale of 10 nanometers. Wherein the polyhedral oligomeric silsesquioxane (Polyhedral Oligomeric Silsesquioxane la, hereinafter 'POSS' hereinafter) to the molecule and represented by the general formula (RSiO _{1 .5) 8,} improving the screen synthesis and solubility of the organic solvent and the organic polymer matrix It consists of seven organic R substituents on the octa core for and eight corners connected by functional groups (eg, noborene, vinyl, (meth) acrylates, etc.) for carrying out chain polymerization.

While achieving diversity in nanosize morphology, liquid crystals [KM Kim and YJ Chujo, J. Polym . Sci . Part A: Polym . Chem . , 39 , 4035 (2001); P. Xie and RB Zhang, Polym. Adv . Techno . , 8 , 649 (1997); CX Zhang, TJ Bunning, and RM Laine, Chem . Mater . , 13 , 3653 (2001)], nanocomposites [J. Choi, J. Harcup, AF Yee, Q. Zhu, and RM Laine, J. Am . Chem . Soc . , 123 , 11420 (2001); C. Sanchez, G. Soler-Illia, F. Ribot, T. Lalot, CR Mayer, and V. Cabuil, Chem . Mater . , 13 , 3061 (2001); L. Zheng, RJ Farris, and EB Coughlin, Macromolecules , 34 , 8034 (2001)], CVD coatings [MD Nyman, SB Desu, and CH Peng, Chem . Mater . , 5 , 1636 (1993)] and photoresists in lithographic techniques [E. Tegou, V. Bellas, E. Gogolides, and P. Argitis, Microelectro . Eng . 73-74 , 238 (2004); KE Gonsalves, L. Merhari, H. Wu, and Y. Hu, Adv . Mater . , 13 , 703 (2001)], in order to create new potential applications, the synthesis of POSS-containing block copolymers with oxidation resistance and high structural integrity at high temperatures compared to non-POSS containing polymers Critically important. However, very few current block copolymers containing POSS nanoparticles have been reported [J. Pyun and K. Matyjaszewski, Macromolecules , 33 , 217 (2000); J. Pyun, K. Matyjaszewski, J. Wu, G.-M. Kim, SB Chun, and PT Mather, Polymer , 44 , 2739 (2003); TS Haddad, PT Mather, HG Jeon, SB Chun, and SH Phillips, Mat . Res . Soc . Symp . Proc . 628 , CC2.6.1 (2000); Y. Kwon and K.-H. Kim, Macromol . Res. , 14 , 424 (2006).

It is an object of the present invention to provide an amphipathic organic / inorganic block copolymer comprising a hydrophobic polyhedral oligomeric silsesquioxane (POSS) segment and a method for preparing the same.

The present invention relates to an amphiphilic organic / inorganic block copolymer including a hydrophobic polyhedral oligomeric silsesquioxane (POSS) segment and a method for preparing the same, and more specifically, to the following formula (1) poly (NBECOOH- -NBEPOSS b) block copolymers and to be directed to a poly (NBETMS- -NBEPOSS b) block copolymers and methods for their preparation represented by the formula (2).

[Formula 1]

[Formula 2]

[In Formula 1 and 2, R is hydrogen, (C1-C20) alkyl or (C3-C20) cycloalkyl; m is 3-20; n is 50 to 150.]

The invention _{RuCl 2 (= CHPh) (PCy} 3) 2 / CH 2 Cl 2/20 ℃ 2- endo-3-exo-5-using system norbornene dicarboxylic acid (2-endo-3-exo -5-Norborene dicarboxylic acid (NBECOOH) and 2-endo-3-exo-5-norbornene-2,3-dicarboxylic acid bis (trimethylsilyl) ester (2-endo-3-exo-5-Norbornene- By hydrolysis of trimethylsilyl groups in poly (NBETMS- b- NBEPOSS) copolymers by using living ring-opening metathesis polymerization of 2,3-dicarboxylic acid bis (trimethylsilyl) ester (NBETMS) and the addition of a continuous NBEPOSS monomer It is characterized by continuously producing a poly (NBECOOH- b- NBEPOSS) copolymer.

The reaction for preparing the poly (NBECOOH- b- NBEPOSS) copolymer according to the present invention is shown in Scheme 1 below.

Scheme 1

[Wherein R is hydrogen, (C1-C20) alkyl or (C3-C20) cycloalkyl; m is 3-20; n is 50 to 150.]

Poly (NBECOOH- b -NBEPOSS) block copolymer represented by the formula (1) is

1) a ring-opening under the conditions of the NBETMS compound of formula _{3 RuCl 2 (= CHPh) (} PCy 3) 2 / CH 2 Cl 2/20 ℃ metathesis polymerization (ring opening metathesis polymerization, ROMP) by reacting poly (NBETMS of formula (IV) ) Preparing a compound;

2) preparing a poly (NBETMS- b- NBEPOSS) block copolymer of Formula 2 by continuously adding NBSPOSS monomer compound of Formula 5 to the poly (NBETMS) compound of Formula 4; And

3) preparing a poly (NBECOOH- b- NBEPOSS) block copolymer of Chemical Formula 1 by hydrolyzing the poly (NBETMS- b- NBEPOSS) block copolymer of Chemical Formula 2 prepared above.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Wherein R is hydrogen, (C1-C20) alkyl or (C3-C20) cycloalkyl; m is 3-20; n is 50 to 150.]

In addition, the NBETMS compound of Formula 3 used as a starting material in the present invention, as shown in Scheme 2 below, by reacting cyclopentadiene and fumaric acid prepared by pyrolysis of dicyclopentadiene to prepare an NBECOOH compound, trimethylsilyl It is prepared by the reaction.

Scheme 2

The structures of the poly (NBECOOH- b- NBEPOSS) block copolymers and poly (NBETMS- b- NBEPOSS) block copolymers prepared in the present invention are characterized using ¹ H NMR, ¹³ C NMR and GC-mass spectrometers.

As mentioned above, the present invention not only provides novel amphiphilic organic / inorganic block copolymers comprising hydrophobic polyhedral oligomeric silsesquioxane (POSS) segments, but also RuCl ₂ (= CHPh). _{) (PCy 3) 2 / CH} 2 Cl 2/20 ℃ 2- endo-3-exo-5-using system norbornene dicarboxylic acid (2-endo-3-exo -5-Norborene dicarboxylic acid, NBECOOH ) And 2-endo-3-exo-5-norbornene-2,3-dicarboxylic acid bis (trimethylsilyl) ester (2-endo-3-exo-5-Norbornene-2,3-dicarboxylic acid bis ( trimethylsilyl) ester, by using an addition reaction of the living ring-opening metathesis polymerization, and subsequently the monomer NBEPOSS NBETMS), poly (NBETMS- -NBEPOSS b) continuously by hydrolysis of the trimethylsilyl group in the copolymer poly (NBECOOH- b -NBEPOSS) copolymers can be readily prepared.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited by the following examples.

EXAMPLE

Reagents (Materials)

Cyclopentyl-POSS-norbornene monomer (NBEPOSS), 1- [2- (5-norbornene-2-yl) ethyl] -3,5,7,9,11,13,15 ^{-Heptacyclopentylpentacyclo} [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] ^{-octasiloxane} (1- [2- (5-norbornene-2-yl) ethyl] -3,5,7 , 9,11,13,15-heptacyclopentylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] -octasiloxane, fumaric acid, chlorotrimethyl silane, ethyl vinyl ether Ethyl vinyl ether, Celite and neutral activated aluminum oxide: Aldrich Chemical Co.

Grubbs catalyst (RuCl ₂ (= CHPh) (PCy ₃ ) _2: Strem Chemical Co.)

Dicyclopentadiene: ACROS

Dichloromethane (DC chemicals, 99.5%): refluxed for at least 12 hours in the presence of CaH ₂ (Calcium hydride) and distilled immediately before use

Diethyl ether (DC chemicals): washed with 10% aqueous sodium sulfite solution and water, dried over magnesium sulfate overnight, filtered and refluxed in the presence of sodium and benzophenone until the color turns blue, and distilled immediately before use.

Pentane (Kanto chemical, Japan): After passing through the silica gel, refluxing for at least 12 hours in the presence of CaH ₂ (Calcium hydride) and distillation immediately before use

Pyridine (Showa chemical, Japan, 99.5%): Molecular sieves of 4Å or more and used after drying for more than 24 hours

Reagents other than above: Aldrich Chemical Co.

Instruments and Measurement

¹ H and ¹³ C NMR spectra were recorded on an Oxford NMR 300 MHz spectrometer. The molecular weight and molecular weight distribution of the synthesized homopolymers and diblock copolymers were determined using a Waters 515 pump and a Waters gel with a Waters 410 differential refractometer connected to two styragel GPC columns (10 ⁴ 10 and 10 ⁵ Å). It was measured at room temperature using permeation chromatography (Waters Gel Permeation Chromatography, GPC). THF was used as the mobile phase at a flow rate of 1 mL / min. Molecular weights were calibrated against narrow molecular weight polystyrene standards. All synthetic procedures were carried out in a nitrogen filled glove box.

[ Example  1] 2- endo 3- Exo -5- Norborneen  Dicarboxylic acid ( NBECOOH ) And 2-endo-3- Exo -5- Norborneen -2,3-dicarboxylic acid Bistrimethylsilyl )ester( NBETMS Manufacturing

NBECOOH Manufacture

100 mL of dicyclopentadiene was placed in a 250 mL three neck round bottom flask and refluxed under nitrogen atmosphere to pyrolyze the dicyclopentadiene into cyclopentadiene. After 5 mL of initial distillation was not recovered, cyclopentadiene was distilled into a vessel cooled to -78 ° C. Fumaric acid (30.0 g, 0.259 mol) was added to 350 mL of methanol, and pyrolysed cyclopentadiene (35.9 mL, 0.431 mol) was added at room temperature. After stirring the reaction mixture overnight, the solvent was removed under reduced pressure to obtain a solid. The obtained solid was washed 5 times with pentane and dried to obtain 46.9 g (99.7%) of the title compound NBECOOH as a white solid.

¹ H NMR ( δ , D ₂ O, 300 MHz): 6.18-6.25 ( dd , 1H, = C H ), 5.87-6.15 ( dd , 1H, = C H ), 3.20 -3.25 ( t , 1H, exo- C H ), 3.15 ( s , 1H, bridge head), 3.04 ( s , 1H, bridge head), 2.44-2.49 ( dd , 1H, endo -C H ), 1.41-1.47 ( d , 1H, C H ₂ ) , 1.31-1.38 ( dd , 1H, C H ₂ ). ¹³ C NMR ( δ , acetone-d ₆ , 75 MHz): 175.7, 174.4, 138.2, 135.9, 48.3, 48.2, 47.9, 47.6, 46.1.

NBETMS Manufacture

The NBECOOH (8.0 g, 44 mmol) prepared above was dissolved in 280 mL of distil.diethyl ether, and 8.7 mL (132 mmol) of pyridine was added at a time. Chlorotrimethylsilane (22.48 mL, 132 mmol) was added over 30 seconds and stirred. A white precipitate of pyridine hydrochloride immediately formed. The precipitate was removed by celite filter and the filtrate was stirred for 3 hours. The solvent was removed under reduced pressure to give 11.5 g (80.1%) of the title compound, NBETMS, as a white solid. Further purification was redissolved the resulting white solid in pentane and passed through a neutral inert alumina column, then the pentane was removed under reduced pressure, and the white solid was recrystallized using diethyl ether.

¹ H NMR (δ, CDCl ₃ , 300 MHz): 6.27-6.30 (dd, 1H, = C H ), 6.03-6.06 (dd, 1H, = C H ), 3.32-3.35 (t, 1H, exo-C H ), 3.22 (s, 1H, bridge head), 3.11 (s, 1H, bridge head), 2.61-2.63 (dd, 1H, endo-C H ), 1.54-1.57 (d, 1H, C H ₂ ), 1.42-1.45 (dd, 1H, C H ₂ ), 0.23-0.28 (d, 18H, TMS). ¹³ C NMR (δ, CDCl ₃ , 75 MHz): 175.2, 174.1, 137.9, 135.1, 49.5, 49.0, 48.0, 47.6, 46.1, 0.0.

Norborneen  Monomer, NBECOOH  And NBETMS Characterization of

NBECOOH and its trimethylsilylated NBETMS were identified by ¹ H, ¹³ C NMR and GC-mass spectrometer. ¹ H NMR spectrum of NBECOOH is shown in FIG. 1. In Figure 1, the characteristic resonance peaks of the vinyl (6,7) peak (-C H = C H- ) of the norbornene-type ring compound were clearly observed at 6.18-6.25 ppm and 5.87-6.15 ppm. Since the carboxylic acid groups are attached at the endo- and exo- positions, the two methane (2, 3) protons adjacent to the carboxylic acid are 3.20-3.25 ppm (exo-C H ) and It was observed at 2.44-2.49 ppm (endo-C H ). In the case of NBETMS prepared by trimethylsilylation of NBECOOH in FIG. 4, all other characteristic peaks remain the same as NBECOOH except for the characteristic resonance signal of trimethylsilyl group (8,9) at 0.23-0.28 ppm. This confirmed trimethylsilylation of NBECOOH. In FIGS. 2 and 5, the structure of the norbornene compound synthesized from ¹³ C NMR spectra of NBECOOH and NBETMS was confirmed. In addition, the molecular ion peak measured by the GC-mass spectrometer confirmed that each monomer was synthesized at 182 for NBECOOH and 326 for NBETMS [FIGS. 3 and 6].

NBETMS is highly reactive and hydrolyzed by moisture in the air. It has also been reported to remove TMS groups by neutral water (RS Saunders, RE Cohen, SJ Wong, and RR Schrock, Macromolecules , 25 , 2055 (1992)). The inventors have found that NBETMS degrades slowly upon storage at −5 ° C. with silica gel in a refrigerator. As shown in FIG. 7, it was observed that as the storage period increased, a new peak appeared between 6.1-6.2 ppm of two vinyl peaks of pure NBETMS, and the storage stability of NBETMS was studied as follows. NBETMS stored for different storage times were transferred into a glove box and dissolved in distilled pentane. The insoluble portion in the pentane was filtered through a pre-dried glass funnel. The fennel was dried and the degraded compounds were separated and weighed. The decomposition rate (wt%) of NBETMS was calculated and FIG. 8 shows the decomposition rate (wt%) according to storage time. 8 shows a relatively slow decomposition rate of 0.206 wt.% / Day.

[ Example  2] Poly ( NBETMS ) And Of poly (NBECOOH)  Produce

Poly (NBECOOH) was prepared by hydrolyzing Poly (NBETMS) prepared by ROMB of NBETMS in a glovebox.

Preparation of Poly (NBETMS)

Two small vials with plastic screw caps were added 2.65 mL of a CH ₂ Cl ₂ solution of 3.68 × 10 ⁻² M NBETMS, respectively, and stirred at 20 ° C. 1.1 mL of a CH ₂ Cl ₂ solution of Grubbs' catalyst ([RuCl ₂ (= CHPh) (PCy ₃ ) ₂ ] = 3.68 × 10 ⁻⁴ M) was added to each vial. The color of the polymerization reaction changed from pink to yellow within 10 minutes. Seven parallel reactions were started at the same time, and the reaction was terminated by injecting 0.9 mL of ethyl vinyl ether into each vial after 1 hour, 2 hours, 3 hours, 4.5 hours, 6 hours, 12 hours, and 24 hours. These were stirred again for 0.5 hours. The ethyl vinyl ether was used in excess of 75 times the initiator to effect efficient termination of the reactive chain ends.

¹ H NMR ( δ , CDCl ₃ , 300 MHz): 5.18-5.54 ( m , 2H, = C H ), 3.14-2.68 ( m , 4H, C H ), 1.92 ( bs , 1H, C H ₂ ), 1.51 ( bs , 1H, C H ₂ ), 0.25 ( bs , 18H, TMS).

Preparation of Poly (NBECOOH)

The vial was taken out of the glovebox, and 1 mL of a hydrolysis aqueous solution containing HCl or acetic acid was added with vigorous stirring to hydrolyze the poly (NBETMS). After 2 hours the solvent was removed and the residue light brown solid was redissolved in 5 mL of THF and then precipitated by the addition of 200 mL of dichloromethane to remove the remaining initiator with vigorous stirring. The resulting precipitate was dried under reduced pressure at 40 ° C. for 24 hours. The product that readily absorbed moisture was immediately transferred to the glovebox, dried and weighed.

¹ H NMR ( δ , THF-d ₈ , 300 MHz): 5.34-5.57 ( m , 2H, = C H ), 2.72-3.21 ( m , 4H, C H ), 2.04 ( bs , 1H, C H ₂ ) , 1.53 ( bs , 1 H, C H ₂ ).

NBETMS of Living ROMP Research on

In order to find optimized living ROMP conditions, ROMP of NBETMS was performed using a reaction temperature of 20 ° C., solvent CH ₂ Cl ₂ and initiator RuCl ₂ (= CHPh) (PCy ₃ ) ₂ . Polymerization conditions are as follows.

[RuCl ₂ (= CHPh) (PCy ₃ ) ₂ ] = 3.68 × 10 ⁻⁴ M

[NBETMS] = 3.68 × 10 ^-2 M

After each period of time, the polymerization was terminated with excess ethyl vinyl ether. The results for ROMP of NBETMS at 20 ° C. are shown in Table 1 below.

TABLE 1 Results for ROMP of NBETMS at 20 ° C ^a

As shown in Table 1 above, the polymerization of NBETMS proceeded smoothly after the addition of the initiator raw material solution and the conversion rate of the monomer reached 100% after 12 hours of reaction.

FIG. 9 shows the ¹ H NMR spectra of NBETMS monomers, poly (NBETMS) and poly (NBECOOH). As the double bonds present in the cyclic norbornene monomers twisted through the ROMP opened up forming new double bonds between the monomers, the vinyl protons in the monomer and polymer exhibited different chemical conditions around the vinyl protons. As a result, the vinyl peak of NBETMS shifted from δ6.0-6.4ppm after ROMP of NBETMS shifted to δ5.0-5.8ppm, indicating the vinyl peak of poly (NBETMS). Thus, complete conversion of NBETMS monomers during polymerization was also confirmed from the ¹ H NMR spectrum. The ¹ H NMR spectrum (THF-d ₈ ) of poly (NBECOOH) produced after hydrolysis of poly (NBETMS) efficiently removes trimethylsilyl groups present in poly (NBETMS) and other characteristic peak values remain intact. Showed.

First order kinetics (ln ([M ₀ ] / [M]) vs. time) plots are shown in FIG. The ratio of proliferation R _P is represented by the following equation (1).

k _p is the polymerization rate constant, [M] is the monomer concentration to withstand the polymerization at a given time (t), [M ₀ ] is the initial monomer concentration, and [I] is the initiator or increased chain terminus. Concentration. If the first kinematic plot shows a linear relationship at a constant temperature, it indicates that the amount of chain ends that is increased is constant, which means that no termination occurs during the polymerization. The linear relationship between ln ([M ₀ ] / [M]) and time for ROMP of NBETMS was observed in FIG. 10, which confirms the absence of termination during ROMP of NBETMS with Grubbs catalyst.

대 전환을 도 11에 도시하였다.

과 상응하는 전환 사이의 관계는 하기 수학식 3으로 표시된다.Another plot to identify the absence of chain transfer reactions.

Large conversion is shown in FIG. 11.

The relationship between and the corresponding conversion is represented by the following equation.

는 고분자의 수 평균 분자량이고, M_m은 단량체의 분자량이고, N_p는 고분자 사슬의 수를 나타낸다.

이 전환에 대해 선형 의존도를 가질 때 N_p는 일정한 것을 의미하고, 전체 중합 반응 동안에 어떠한 연쇄이동반응이 일어나지 않았음을 나타낸다. 도 11에 나타낸 바와 같이 선형

대 전화 플롯이 관찰되었고 이는 연쇄이동반응의 부재를 나타낸다. 폴리(NBETMS)에 있는 트리메틸실릴기는 수분과의 반응성이 너무 좋아 폴리(NBETMS) 자체의 정확한 분자량을 GPC를 사용하여 측정할 수 없다. 따라서, 고분자 전구체, 폴리(NBETMS)의 가수분해 후 생성된 폴 리(NBECOOH)의 분자량이 상기 표 1 및 도 11에 나타낸 바와 같이 측정되었다. 도 12은 좁은 분자량 분포를 유지하는 동안 증가되는 전환에 따른 높은 분자량으로의 GPC 흔적량의 이동을 도시화한 것이다. 그결과 모든 고분자 사슬 말단은 종결 및 연쇄이동 반응과 같은 사슬끊김반응 없이 증가되었다.

Is the number average molecular weight of the polymer, M _m is the molecular weight of the monomer, and N _p represents the number of polymer chains.

When having a linear dependence on this conversion, N _p means constant, indicating that no chain transfer reaction occurred during the entire polymerization reaction. Linear as shown in FIG.

Large plots were observed, indicating the absence of chain transfer reactions. The trimethylsilyl group in poly (NBETMS) is so reactive with water that the exact molecular weight of poly (NBETMS) itself cannot be measured using GPC. Therefore, the molecular weight of poly (NBECOOH) produced after the hydrolysis of the polymer precursor, poly (NBETMS) was measured as shown in Table 1 and FIG. FIG. 12 depicts the shift of GPC traces to higher molecular weights with increasing conversion while maintaining a narrow molecular weight distribution. As a result, all polymer chain ends were increased without chain breakage reactions such as termination and chain transfer reactions.

A second NBETMS increase was added to the polymerization mixture and maintained for 24 hours to see if the poly (NBETMS) chain ends remained active after complete conversion of the NBETMS monomer. Polymerization conditions were as follows.

Primary [NBETMS] = 3.68 × 10 ^-2 M, [RuCl ₂ (= CHPh) (PCy ₃ ) ₂ ] = 7.36 × 10 ^-4 M

2nd [NBETMS] = 3.68 × 10 ^-2 M

=11,300g/몰,

=1.23을 나타내었으나, 2차 NBETMS 증가량을 첨가시킨 후 합성된 폴리(NBETMS)는 더 높은 분자량(

=23,300g/몰) 및 좁은 분자량 분포(

=1.23)을 향하여 이동하였다. 이는 증가되는 사슬 말단은 첫 번째 블록의 중합반응 후에도 여전히 활성을 띠고 있다는 것을 나타낸다. 상기 결과들로부터 일정한 조건하에서 NBETMS의 ROMP는 리빙 방식으로 진행됨을 알 수 있다.The first synthesized poly (NBETMS) from GPC results is

= 11,300 g / mol,

= 1.23, but the poly (NBETMS) synthesized after adding the second NBETMS increase was higher molecular weight (

= 23,300 g / mol) and narrow molecular weight distribution (

= 1.23). This indicates that the increasing chain ends are still active after the polymerization of the first block. From the above results, it can be seen that the ROMP of NBETMS proceeds in a living manner under certain conditions.

[ Example  3] through continuous monomer addition Poly (NBECOOH- b -NBEPOSS)  Produce

Poly (NBECOOH- b- NBEPOSS) was added to NBEPOSS raw material solution in the poly (NBETMS) block prepared in Example 1 continuously in the content shown in Table 2 and stirred for 2 hours and then 50 μL of ethyl vinyl ether Injection was completed to terminate the reaction to prepare poly (NBETMS- b- NBEPOSS). 500 μL of the prepared poly (NBETMS- b- NBEPOSS) was taken and subjected to ¹ H NMR analysis. The reaction mixture was stirred for 0.5 hour for complete termination. After 150 μL of acetic acid was added to the reaction mixture, the reaction mixture was repeatedly dissolved / precipitated in THF / CH ₂ Cl ₂ and filtered repeatedly.

TABLE 2 Properties of Poly (NBECOOH- b- NBEPOSS) Copolymer Prepared via Continuous ROMP ^a

Table 2 shows the characteristics of the poly (NBECOOH- b- NBEPOSS) copolymer.

Poly (NBECOOH- -NBEPOSS b) for the synthesis of the copolymer, subject to the living ROMP of NBETMS using _{NBETMS / RuCl 2 (= CHPh)} (PCy 3) 2 / CH 2 Cl 2/20 ℃ system poly (NBETMS) It was first performed to obtain. After complete conversion of NBETMS, NBEPOSS was added continuously to the reaction and the poly (NBETMS- b- NBEPOSS) was hydrolyzed to form a poly (NBECOOH- b- NBEPOSS) copolymer. The polymerization was terminated by the addition of ethyl vinyl ether immediately after the complete conversion of the second monomer NBEPOSS to minimize the in-chain cross-interchange reaction of the last block copolymer. Series of poly (NBECOOH- -NBEPOSS b) copolymer was synthesized in a different NBEPOSS content of the three. The results of homopolymerization of NBETMS are shown in Table 2 above. GPC traces of poly (NBECOOH- b- NBEPOSS) copolymers with different NBEPOSS contents and their precursor poly (NBECOOH) homopolymers are shown in FIG. 13. Poly (NBECOOH- b -NBEPOSS) copolymer from Figure 13 was moved while maintaining a narrow molecular weight distribution towards higher molecular weight according to the content of NBEPOSS.

The structure of NBEPOSS in the block copolymer was determined using ¹ H NMR as shown in FIG. 14. The signal intensity ratio of the vinyl peaks between the poly (NBETMS) block and the poly (NBEPOSS) block was shown at δ 5.18-5.55 ppm and the cyclopentyl protons from the poly (NBEPOSS) block at δ 1.30-1.50 ppm. The calculated content of NBEPOSS in the block copolymer was consistent with the feed rate of the monomers. Exhibited 15 poly (NBETMS) and poly (NBETMS- -NBEPOSS b) a poly (NBECOOH) and poly each ¹ H NMR (NBECOOH- b -NBEPOSS) copolymers prepared by the hydrolysis of the copolymer. Trimethylsilyl groups in the poly (NBETMS) block show quantitative removal after hydrolysis. Small peaks remaining around δ 0 ppm are expected to contribute from the proton peaks beside the Si atoms present in the POSS.

In the present invention, an amphiphilic organic / inorganic hybrid poly (NBECOOH- -NBEPOSS b) copolymers _{RuCl 2 (= CHPh) (PCy} 3) 2 / CH 2 Cl 2/20 ℃ using the system NBETMS and continuous ROMP of NBEPOSS It is prepared by hydrolyzing the poly (NBETMS- b -NBEPOSS) copolymer prepared by.

Firstly, ROMB of NBETMS was conducted to examine its living behavior, which required the synthesis of block copolymers by continuous monomer addition techniques. Because of the relatively low storage instability of NBETMS, living poly (NBETMS) is produced from the synthesized NBETMS without termination and chain transfer reactions to control the rich and narrow molecular weight distribution. The living nature of poly (NBETMS) chain ends under monomer depleted conditions was confirmed by using increased monomer addition methods. The poly (NBECOOH- b- NBEPOSS) copolymer was then prepared by hydrolysis of the trimethylsilyl group in the poly (NBETMS- b -NBEPOSS) copolymer after the continuous monomer addition of NBEPOSS to the living poly (NBETMS).

¹ H NMR spectrum of NBECOOH (in D ₂ O) - 1

2- ¹³ C NMR spectrum of NBECOOH (in acetone-d ₆ )

Figure 3-GC Mass Spectrum of NBECOOH

¹ H NMR spectrum of NBETMS (in CDCl ₃₎ - 4

5- ¹³ C NMR spectrum of NBETMS (in CDCl ₃ )

Figure 6-GC Mass Spectrum of NBETMS

Figure 7 - ¹ H NMR spectrum of NBETMS for the identification of the degraded compound (- a monosubstituted NBETMS phase; HA-pure NBETMS)

Figure 8-Degradation rate of NBETMS

Figure 9 - NBETMS monomers, poly (NBETMS) ¹ H NMR spectrum of the precursor and poly (NBECOOH)

FIG. 10-Phone and ln ([M] 0 / [M]) vs. Time Plot in ROMP of NBETMS [○: Transition, ●: ln ([M] ₀ / [M])]

) 대 전환의 플롯11-Number average molecular weight for ROMP of NBETMS (

) Vs. plot

12-Shift of GPC curve of poly (NBECOOH) with time increase

Figure 13-GPC curves of poly (NBECOOH) and poly (NBECOOH- b- NBEPOSS) copolymers

14 - Poly (NBETMS) ¹ H NMR spectrum of the homopolymer and the poly (NBETMS- b -NBEPOSS) copolymer

15 - Poly (NBECOOH) ¹ H NMR spectrum of the homopolymer and the poly (NBECOOH- -NBEPOSS b) copolymer

Claims (4)

Poly (NBECOOH- b -NBEPOSS) block copolymer represented by the formula (1). [Formula 1]

[Wherein R is hydrogen, (C1-C20) alkyl or (C3-C20) cycloalkyl; m is 3-20; n is 50 to 150.] Poly (NBETMS- b- NBEPOSS) block copolymer represented by the formula (2). [Formula 2]

[Wherein R is hydrogen, (C1-C20) alkyl or (C3-C20) cycloalkyl; m is 3-20; n is 50 to 150.] 1) a ring-opening under the conditions of the NBETMS compound of formula _{3 RuCl 2 (= CHPh) (} PCy 3) 2 / CH 2 Cl 2/20 ℃ metathesis polymerization (ring opening metathesis polymerization, ROMP) by reacting poly (NBETMS of formula (IV) ) Preparing a compound; 2) preparing a poly (NBETMS- b- NBEPOSS) block copolymer of Formula 2 by continuously adding NBSPOSS monomer compound of Formula 5 to the poly (NBETMS) compound of Formula 4; And 3) step of hydrolyzing the poly (NBETMS- b -NBEPOSS) block copolymer of the general formula (2) prepared above prepared poly (NBECOOH- b -NBEPOSS) block copolymer of the formula (1); poly of the formula (1), characterized in the (NBECOOH- b -NBEPOSS) A method for preparing a block copolymer. [Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Wherein R is hydrogen, (C1-C20) alkyl or (C3-C20) cycloalkyl; m is 3-20; n is 50 to 150.] 1) a ring-opening under the conditions of the NBETMS compound of formula _{3 RuCl 2 (= CHPh) (} PCy 3) 2 / CH 2 Cl 2/20 ℃ metathesis polymerization (ring opening metathesis polymerization, ROMP) by reacting poly (NBETMS of formula (IV) ) Preparing a compound; And 2) preparing a poly (NBETMS- b- NBEPOSS) block copolymer of Chemical Formula 2 by continuously adding the NBSPOSS monomer compound of Chemical Formula 5 to the poly (NBETMS) compound of Chemical Formula 4 prepared above; A process for preparing a poly (NBETMS- b- NBEPOSS) block copolymer of formula (2). [Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Wherein R is hydrogen, (C1-C20) alkyl or (C3-C20) cycloalkyl; m is 3-20; n is 50 to 150.]

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