Living Radical Polymerization - American Chemical Society

Chapter 3

Stereospecific Living Radical Polymerization 1

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Masami Kamigaito , Kotaro Satoh , Decheng Wan , Yuya Sugiyama , Kazuhiko Koumura , Takuya Shibata , and Yoshio Okamoto 1

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Downloaded by UNIV OF GUELPH LIBRARY on August 9, 2012 | http://pubs.acs.org Publication Date: September 7, 2006 | doi: 10.1021/bk-2006-0944.ch003

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1

Department of Applied Chemistry, Graduate School of Engineering, and Eco Topia Science Institute, Nagoya University, Nagoya 464-8603, Japan

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The simultaneous control of the molecular weights and tacticity was attained by several appropriate combinations of a controlled/living radical polymerization and a stereospecific radical polymerization. They included the ruthenium- and iron-catalyzed living radical polymerizations of methacrylates and acrylamides in polar solvents and in the presence of metal triflates, respectively, the iodine-transfer radical polymerization of vinyl acetate in fluoroalcohols, and the radical polymerization of N-vinylpyrrolidone with RAFT/MADIX agents in fluoroalcohols. In each case, the combined system can give polymers with controlled molecular weights and a high iso- or syndiotacticity.

Introduction The simultaneous control of the molecular weights and stereochemistry of a polymer chain is one of the most challenging targets in radical polymerization although either is now achievable by many methods (Scheme 1). Specifically for controlling the molecular weights, there have been significant developments over the past 10 years, which can produce polymers with the molecular weights controlled by the monomer to initiator ratio and narrow molecular weight distributions (MWDs) (1). Some of the systems are 26

© 2006 American Chemical Society

In Controlled/Living Radical Polymerization; Matyjaszewski, K.; ACS Symposium Series; American Chemical Society: Washington, DC, 2006.


27 versatile and available for various vinyl monomers. The representative polymerizations are the nitroxide-mediated polymerization (NMP) (2,3), metalcatalyzed living radical polymerization or atom transfer radical polymerization (ATRP) (4-8), and polymerization controlled by reversible addition fragmentation chain transfer (RAFT) (9) or macromolecular design via the interchange of xanthates (MADIX) (10). The concept or the strategy for controlling the molecular weights is common, namely, to introduce the dormant species that can rapidly interchange with the growing radical species with the aid of some stimulus such as heat, catalyst, or radical generator. In comparison to a large number of examples concerning the molecular weight control, there are not very many for controlling the tacticity of the polymers. However, in more recent years, general methods for controlling the tacticity in radical polymerization of various polar monomers have been developed (11). They rely on the use of polar solvents or Lewis acid additives that can interact with the substituents of the monomer or the growing terminal via hydrogen-bonding or coordination. For example, a bulky and protic fluoroalcohol affords syndiotactic polymers from vinyl acetate (12) and methyl methacrylate (13) while a metal triflate or MgBr gives isotactic polymers in (meth)acrylamide (14) and methacrylate (15, 16) polymerizations. 2

Controlled/Living Radical Polymn ÎNMP/SFRPl — ΛΛΛΛΛΛΛΛ/ Q — Q

/>

Stereospecific Radical Polymn f Solvent-Mediated]

— ^

V ATRP/Metal-Catalyzed

RAFT/MADIX] xwwwwC—SCZ

+ R*

II

s Iodine Transfer) ΛΛΛΛΛΛΛΛ/

C-l

+ R'

Scheme 1. Several systems for controlled/living radical polymerization and stereospecific radical polymerization. These developments more or less suggest one to examine the simultaneous control of the molecular weights and tacticity by effectively combining the living and stereospecific radical polymerizations. The key to the success is to find



28 appropriate combinations where one of the controls should not be lost by the other component. Although several effective combinations have already been reported for a few monomers, it is still unclear which combination is desirable and applicable for certain types of monomers (17-20). This article is an overview of our quite recent results on stereospecific living radical polymerizations that can simultaneously control the molecular weights and tacticity. They include (1) the ruthenium-catalyzed living radical polymerizations of methacrylates influoroalcohols,(2) the iron-catalyzed living radical polymerizations of acrylamides in the presence of metal triflates, (3) the iodine-transfer radical polymerizations of vinyl acetate influoroalcohols,and (4) the xanthate-mediated radical polymerizations of ΛΓ-vinylpyrrolidone in fluoroalcohols.

Results and Discussion Ruthenium-Catalyzed Systems in Fluoroalcohols for Methyl Methacrylate As we have shown that RuCl (PPh ) is tolerant to various polar solvents like methanol and water and can induce the living radical polymerization of methyl methacrylate (MMA) even in such solvents (21), we first examined the ruthenium complex in a protic and bulky fluoroalcohol [(CF ) COH] for the possible syndiospecific living radical polymerization of M M A (Scheme 2). 2

3

3

3

3

Monomers: CH 3

CH =C ι C=0 2

-C-OH

[MMA O C H J 3

Scheme 2. Ruthenium-catalyzed living radical polymerization in fluoroalcohols As shown in Figure 1, RuCl (PPh ) induced a faster polymerization in the fluoroalcohol at 60 °C than in toluene at 80 °C. Under the same conditions, the indenyl complex [Ru(Ind)Cl(PPh ) ] led to a much faster polymerization. The number-average molecular weights (M ) of the obtained polymers were close to the calculated values assuming that one molecule of the initiator [Me2C(C02Me)CH2C(C0 Me)(Me)Cl] generates one living polymer chain. The 2

3

3

3 2

n

2


29 MWDs of the polymers were relatively narrow. Therefore, these ruthenium catalysts show higher activities in the fluoroalcohol and still maintain their control of the polymer molecular weights. Furthermore, the polymers obtained using RuCl (PPh ) in (CF ) COH had a higher syndiotacticity (rr = 68%) than with the same catalyst in toluene (rr = 63%). Thus (CF ) COH generated the syndiotactic PMMA even with the ruthenium-catalyzed system, where the was almost the same as that with the AIBN-induced system (13). 2

3

3

3

3


3

3

Figure 1. Polymerization ofMMA with RuCl (PPh ) (J) and Ru(Ind)Cl(PPh ) (E) in (CF ) COH at 60 °C: [M] = 2.0 M; [(MMA) -Cl] = 20 mM; [Ru ] = 10 mM; [n-Bu N] = 40 mM. The dashed line is for the polymerization with RuCl (PPh ) in toluene at 80 °C with the same reagent concentrations. 2

3

3

3

n

3

3

0

3

2

3

2

0

0

0

3

A further improvement was accomplished using RuCp*Cl(PPh ) (22) in another bulky fluoroalcohol [(CF ) C(Ph)OH] at a lower temperature (Figure 2). 3

3

2

2

Figure 2. Polymerization of MMA with RuCp*Cl(PPh ) in (CF ) C(Ph)OH: [M] = 2.0 M; [(MMA)r-Cl] = 20 mM; [Ru ] = 4.0 mM; [n-Bu N) = 40 mM. 3

2

3

u

0

0

0

3

0


2

2

30 The Cp*-complex led to efficient polymerizations even at 0 °C to give polymers with controlled molecular weights in agreement with the calculated values and very narrow MWDs (MJM < 1.1). The triad racemo content (rr) increased with the decreasing temperature and reached 76% at 0 °C. These results indicate that the ruthenium-catalyzed living radical polymerization proceeds via a syndiospecific chain growth to afford polymers with controlled molecular weights and high syndiotacticity. n


Iron-Catalyzed Systems with Metal Triflates for Acrylamides Among the variety of iron catalysts effective for the living radical polymerizations, an iron(I) complex, [FeCp(CO) ] , is one of the most active and versatile and is especially effective for the fast living radical polymerization of acrylates and acrylamides (23). The Cp-based iron carbonyl complexes are exclusively tolerant to water unlike the other iron catalysts such as FeBr (PPh ) for the living radical polymerization (24). On the other hand, the isospecific radical polymerization of (meth)acrylamides was reported with the use of metal triflates such as Y(OTf) and Yb(OTf) especially in MeOH, where the highly isotactic polymer was obtained (m = 90%) (14). The added Lewis acid most probably coordinates to the carbonyl groups of the growing polymer chain end and/or monomer to restrict the free rotation of the sp -Vkt growing carbon radical species and results in isospecific chain growth (25). Thus we employed [FeCp(CO) ] in the presence of Y(OTf) for the possible isospecific living radical polymerization of W,Af-dimethylacrylamide (DMAM) (Scheme 3) (26). 2

2

2

3

3

2

3

2

2

2

3

Monomers:

Metal Catalysts:

Ο

CH =CH 2

C,

J

C=0 DMAM NMe

Lewis Acids: Yb(OTf) Y(OTf) Sc(OTf) Y(NTf ) 3

3

3

2

2 3

Scheme 3. Iron-catalyzed living radical polymerization with Lewis acid. Upon the addition of Y(OTf) into the iron-based living radical system (Me C(C0 Et)I/[FeCp(CO) ] /I ) in toluene/methanol (1/1 v/v), the polymerization was drastically accelerated and reached a 96% conversion within 1 h. A similar acceleration was observed in the AIBN-initiated conventional 3

2

2

2

2

2


31 radical polymerization using the same monomer due to the coordination of the Lewis acid to the growing polymer terminal and monomer. The iron(I) complex thus survives even in the presence of the metal triflate in MeOH and possesses the ability of efficiently forming the polymers. The M of the polymers increased in direct proportion to monomer conversion and agreed well with the calculated values (Figure 3). The MWDs were broader in the presence of Y(OTf) probably due to the fast propagation of the radical species originating from the coordination of the Lewis acid. n


3

Figure 3. Polymerization ofDMAM with [FeCp(CO) ] at 60 °C: [M] = 4.0 M; [Me C(CO Et)I] = 40 mM; [Fe ] = 40 mM; [I ] = 20 mM; [Y(OTf) ] = 0 or 200 mM. 2

2

Q

l

2

2

0

0

2

0

3

0

The meso-dyad content (m) of the polymers obtained with [FeCp(CO) ]2 and Y(OTf) was 82%, being as high as that obtained in AIBN and Y(OTf) under similar conditions (Figure 4). 2

3

4.0

3

3.0

2.0

1.0 ppm

2.0

1.5

1.0 ppm K K

l

Figure 4. HNMR Spectra (in DMSO-d ,at 170 °C) ofpoly(DMAM) obtained with the Fé-based system in the absence and presence ofY(OTf) at 60 °C. 6

3


32 These results indicate that both the iron and the yttrium catalysts fulfill their roles to result in polymers with controlled molecular weights and high isotacticity. A similar system was also reported for the combination of CuBr and Y(OTf) while the polymerization seemed to stop around 50% conversion probably due to the loss of the activity of the copper catalyst (18). Therefore, the iron(I) catalyst shows a relatively high activity although the polymerization may also proceed via an iodine-transfer mechanism. 3


Iodine-Transfer Radical Polymerization in Fluoroalcohols for Vinyl Acetate Vinyl acetate (VAc) is a unique vinyl monomer that can be polymerized only via a radical mechanism into high molecular weight polymers while the polymer is familiar as the precursor of polyvinyl alcohol). Since the molecular weights and the tacticity of polyvinyl alcohol) significantly affect the polymer property, the control of the radical polymerization of VAc is valued from the viewpoint of not only fundamental but also industrial chemistry. However, the unconjugated vinyl group renders the control very difficult in comparison to conjugated monomers because the resulting radical species is highly reactive resulting in rapid propagation and some inherent side reactions. Irrespective of such tough situations, there have been several effective systems for controlling the molecular weights and tacticity. Among those for controlling the molecular weights, which now include iodine-transfer (27), iron-catalyzed (23c), RAFT/MADIX (29-34), organotellurium (35), and cobalt-mediated (36,37) radical polymerizations, the iodine-transfer radical polymerization is one of the simplest due to the easily accessible initiating species consisting of an alkyl iodide and a radical generator. For controlling the steric structure, some bulky and protic fluoroalcohols are highly effective in leading to the syndiospecific radical polymerization of VAc (12). Herein, we investigated the iodine-transfer radical polymerization in several fluoroalcohols (Scheme 4) (38).

ry Monomers: CH =CH 2

VAc

Iodide:

CF

2

0

C=0

C=0

OCH CH

CH

Solvents:

CH -I

CF

3

3

CF

3

HO. /

C F 3

C

c

HC-OH CF -C ι · CF 3

2

3

f°Γ^3. O H | C CF 3

3

3

Scheme 4. Iodine-transfer radical polymerization of VAc in fluoroalcohols.


33 The iodine-transfer radical polymerization of VAc was investigated in (CF ) COH, (CF ) CHOH, (CF ) C(Ph)OH, and w-C H [C(CF ) OH] at 20 °C with V-70 [MeOCMe CH CMe(CN)N=NCMe(CN)CH CMe OMe]as the azobased low-temperature radical initiator. In all the solvents, the polymerization smoothly occurred (Figure 5). The initial rate in the three fluoroalcohols except for hexafluoroisopropanol was greater than in the bulk while the final conversions were lower. The MWDs of the polymers depend on the fluoroalcohols and became broader in the following order: w-C H [C(CF ) OH] (MJM = 1.20) < (CF ) C(Ph)OH (1.46) ~ (CF ) COH (1.46) < bulk (1.73) < (CF ) CHOH (2.67). In most of the fluoroalcohols, the molecular weight control was better than in the bulk, where the best molecular weight control was achieved with the fluorodiol (MJM = 1.20). The polymerization in (CF ) CHOH apparently suffers from some side reactions. 3

3

3

2

3

2

2

6

2

4

2

3

6


n

3

2

3

2

3

2

3

2

2

2

4

3

2

2

3

n

m-C H {C(CF3)20H}2 6

0

100

200 Tlme(h)

4

300

• 10

4

3

10

Solvent

(CF ) C(Ph)OH 3 2

• 10

5

MW(PSt)

— I 10

4

10

3

Figure 5. Iodine-transfer radical polymerization of VAc in fluoroalcohols at 20 °C: [M] = 2.0 M; [CH (CO Et)I] = 20 mM; [V-70] = 40 mM; VAc/fluoroalcohol = 1/4 (v/v). 0

2

2

0

0

Figure 6 shows the typical *H NMR spectra of poly(VAc) and poly(vinyl alcohol) obtained by saponification. The tacticity of polyvinyl alcohol) can be calculated from the hydroxyl protons at 4-5 ppm. As summarized in the inset table in Figure 6, all the fluoroalcohols gave a high syndiotacticity in comparison with that in the bulk. The fluorodiol also proved effective for the syndiotactic polymerization similar to (CF ) COH. Specifically, in w-C H [C(CF ) OH] , the simultaneous control of the molecular weight and tacticity was most efficiently attained. 3

3

6

4

3


2

2

34 -fcHj-ÇH-)-

CH

5.0

4.0

-{-CH -ÇH—)2

3

3.0

HO

2.0

CF

3

5.0

ppm

FC 3

O H

OH I CF -C-CF 3

1.0 ppm

4.0

OH

Ç>H

3


Fluoroalcohol

1.46

1.20

MJM

n

58.7

59.0

Tacticity /*(%)

1.46

2.67

1.73

60.4

58.5

52.3

Figure 6. *HNMR Spectra ofpoly(VAc) and polyvinyl alcohol) obtained with iodine-transfer radical polymerization influoroalcoholsat 20 °C and the control of molecular weight and tacticity.

RAFT/MADIX Polymerization in Fluoroalcohols for TV-Vinylpyrrolidone N-Vinylpyrrolidone (NVP) is another unconjugated vinyl monomer, from which high molecular weight polymers are obtained only by radical polymerization. In contrast to the wide applicability of the polymers as non toxic polymers, only a few examples of the controlled polymerizations have been reported for this monomer (lie,39) due to the highly reactive radical species and the polar substituents. Thus we investigated the control of the molecular weight and tacticity using xanthates and fluoroalcohols, respectively, and then combined them together for the simultaneous control (Scheme 5) (40).

RAFT/MADIX: R-CH-S-C-OCH CH

Monomers: CH =CH

2

2

( ÇF Solvents: CF -C-OH

3

3

3

I NVP

\

/

R = H, CH

3

CF

CF

3

H-C-OH I

3

CF

3

Scheme 5.RAFT/MADIXpolymerization ofNVP in fluoroalcohols.


35 The AIBN-initiated bulk radical polymerization of NVP was first investigated in the absence and the presence of xanthates at 60 °C. The use of xanthates slightly retarded the radical polymerization as usually observed in the RAFT polymerization of other monomers (Figure 7). The molecular weights of the polymers obtained with these xanthates increased as the polymerization proceeded. Especially, with the xanthate possessing the 1-phenylethyl fragment, the M increased in direct proportion to polymer yield and agreed well with the calculated values assuming that one molecule of the polymer chain is generated from one molecule of xanthate.


n

I

,

ι

Q J

R = CH

·

G: None E:R = H J :R = C H

4

1

3

n

n

a-~^-

Γ /

u Yield MJM

u Yield MJM

R = H

-|

3

ι

l

30 MW(PMMA)

MW(PMMA)

Figure 7. Xanthate-mediated polymerization ofNVP in bulk at 60 °C: [M] = 9.5 M; [xanthate]ο = 63 mM; [AIBN] = 13 mM. 0

0

Table L Free Radical Polymerization of NVP in Fluoroalcohols

Solvent

Temp., °C 60 60 60 60 20 20 20 20

Bulk CF CH OH (CF ) CHOH (CF ) COH Bulk CF CH OH (CF ) CHOH (CF ) COH 3

3

2

3

3

3

2

3

3

3

2

c

M„"

MJM„

r, %

135 200 116 200 149 500 121 200 126 900 130 000 164 000 92 400

3.11 2.96 3.05 2.89 4.79 3.11 2.30 3.36

53.5 54.5 55.6 58.0 53.5 54.6 55.8 59.0

Yield, % 58 59 57 36 58 65 73 83

2

b

0

a

Polymerization conditions: fluoroalcohol/NVP = 1.65/1 v/v, in the presence of 1% (based on monomer) AIBN, reaction time: 12 h (60 °C), 36 h (20 °C), reaction at 20 °C was under UV irradiation. (400-W high-pressure mercury lamp).

* Determined by SEC in DMF containing 0.1 M LiCl. 0

13

Determined by C NMR in D 0 at 84 °C. 2


36 As for the tacticity control, three fluoroalcohols [CF CH OH, (CF ) CHOH, (CF ) COH] were employed for possible stereoregulation. An increase in the number of CF -groups, bulkiness, and acidity increased the syndiotacticity of the resulting poly(NVP) (Table I). Specifically, in (CF ) COH at a low temperature (20 °C), the highest racemo content was attained (r = 59.0%). The simultaneous control of the molecular weight and tacticity was then examined using the phenylethyl-type xanthate in (CF ) COH at 20 °C. The obtained polymer had controlled molecular weights (M = 12600), narrow MWDs (MJM = 1.28), and a high syndiotacticity (r = 59.8%). 3

3

2

3

2

3

3

3

3

3

3

n


n

Conclusions The simultaneous control of the molecular weights and tacticity was attained by various combinations of the living and stereospecific radical polymerization of several monomers (Table II). The simultaneous control for each monomer has now been achieved by a specific combination of the systems indicated by a gray-colored cell in the table. Although the judicious choice of the reagents and reaction conditions is necessary for the precise control of both, the stereospecific living radical polymerization would provide fruitful developments in precision polymer synthesis and functional materials.

Table II. Status Quo of Living and Stereospecific Radical Polymerization

: Not Attained or Not Studied


37 Acknowledgment


This work was supported in part by the 21st Century Program "NatureGuided Materials Processing" and a Grant-in-Aid for Scientific Research (B) No. 16350062 and Priority Areas "Advanced Molecular Transformations of Carbon Resources" from the Ministry of Education, Culture, Sports, Science and Technology, Japan, the Mitsubishi Foundation, and Tokuyama Science Foundation.

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Living Radical Polymerization - American Chemical Society

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