Sequence controlled methacrylic multiblock Sequence ......Instrumentation. 1H NMR spectra were recorded on Bruker DPX-300 and HD-400 spectrometers using a mixture of deuterated chloroform

NATURE CHEMISTRY | www.nature.com/naturechemistry 1

SUPPLEMENTARY INFORMATIONDOI: 10.1038/NCHEM.2634

1

Sequence-controlled methacrylic multiblock

copolymers via sulfur-free RAFT emulsion

polymerization

Nikolaos G. Engelis† a, Athina Anastasaki*† a,b ,Gabit Nurumbetov a, Nghia P. Truongb, Vasiliki

Nikolaoua, Ataulla Shegiwala, Michael R. Whittakerb, Thomas P. Davis* b and David M. Haddleton* a,b

a - University of Warwick, Chemistry Department, Library road, CV4 7AL, Coventry, United

Kingdom.

b - ARC Centre of Excellence in Convergent Bio-Nano Science and Technology, Monash Institute of

Pharmaceutical Sciences, Monash University (Parkville Campus), 399 Royal Parade, Parkville,

Victoria 3152, Australia

†These authors contributed equally to this work.

Table of contents

1.Materials/Instrumentation p2

2.Synthetic protocols p3

3.Supplementary tables and figures p4

4.Supplementary references p18

1

Sequence controlled methacrylic multiblock

copolymers via sulfur free RAFT emulsion

polymerization

Nikolaos G. Engelis† a, Athina Anastasaki*† a,b ,Gabit Nurumbetov a, Nghia P. Truongb, Vasiliki

Nikolaoua, Ataulla Shegiwala, Michael R. Whittakerb, Thomas P. Davis* b and David M. Haddleton* a,b

a - University of Warwick, Chemistry Department, Library road, CV4 7AL, Coventry, United

Kingdom.

b - ARC Centre of Excellence in Convergent Bio-Nano Science and Technology, Monash Institute of

Pharmaceutical Sciences, Monash University (Parkville Campus), 399 Royal Parade, Parkville,

Victoria 3152, Australia

†These authors contributed equally to this work.

Table of contents

1.Materials/Instrumentation p2

2.Synthetic protocols p3

3.Supplementary tables and figures p4

4.Supplementary references p18

© 2016 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.



2

Section A. Materials / Instrumentation

All reagents were purchased from Sigma-Aldrich or MP Biomedicals and used without further

purification unless otherwise stated. Bis[(difluoroboryl) dimethylglyoximato]cobalt(II) (CoBF) was

synthesised according to the procedure of Espenson. 4,4’-Azobis cyanovaleric acid (CVA) was

employed for the synthesis of the initial PMMA macromonomer while potassium persulfate was used

for all chain extension reactions. Sodium dodecyl sulphate (SDS) was employed as surfactant.

Deionised water (RO grade) was used in all reactions.

Instrumentation. 1H NMR spectra were recorded on Bruker DPX-300 and HD-400 spectrometers

using a mixture of deuterated chloroform and deuterated acetone (v/v=3:2), both obtained from

Aldrich. Chemical shifts are given in ppm downfield from the internal standard tetramethylsilane.

Size exclusion chromatography (SEC) measurements were conducted using an Agilent 1260 GPC-

MDS fitted with differential refractive index (DRI), light scattering (LS) and viscometry (VS)

detectors equipped with 2 x PLgel 5 mm mixed-D columns (300 x 7.5 mm), 1 x PLgel 5 mm guard

column (50 x 7.5 mm) and autosampler. Narrow linear poly(methyl methacrylate) standards in range

of 200-1.0 x 106 g mol-1 were used to calibrate the system. All samples were passed through 0.45 μm

PTFE filter before analysis. The mobile phase was chloroform with 2% triethylamine at a flow rate of

1.0 mL/min. SEC data were analysed using Cirrus v3.3. Matrix-assisted laser desorption ionization

mass spectrometry (MALDI-ToF-MS) was conducted using a Bruker Daltonics Ultra flex II MALDI-

ToF-MS mass spectrometer, equipped with a nitrogen laser delivering 2 ns laser pulses at 337 nm

with positive ion ToF detection performed using an accelerating voltage of 25 kV. Solutions in

tetrahydrofuran (50 μL) of 2,5-dihydroxybenzoic acid (DHB) as matrix (saturated solution), sodium

iodide as cationization agent (1.0 mg/mL), and sample (1.0 mg/mL) were mixed, and 0.7 μL of the

mixture was applied to the target plate. Spectra were recorded in reflector mode calibrating PEG-Me

1100 kDa. DLS measurements were performed on a Malvern instrument Zetasizer Nano Series

instrument with a detection angle of 173°, where the intensity weighted mean hydrodynamic size (Z-

average) and the width of the particle size distribution were obtained from analysis of the




3

autocorrelation function. 1μL of latex was diluted with 1 mL of deionized water previously filtered

with 0.20 μm membrane to ensure the minimization of dust and other particulates. At least 3

measurements at 25 °C were made for each sample with an equilibrium time of 2 min before staring

measurement.

Section B. Synthetic Protocols

1) PMMA Macromonomer Synthesis

In a typical CCTP in emulsion, CoBF (7.5 mg) was placed in a 100 mL round bottom flask together

with a stirring bar. Nitrogen was purged in the flask for at least 1h. Subsequently, MMA (20 mL,

18.72 g, 186.98 mmol) previously degassed for 30 min was added to the flask via a degassed syringe.

The mixture was vigorously stirred under inert atmosphere until total dissolution of the catalyst.

Meanwhile, CVA (0.5 g, 1.7839 mmol), SDS (0.3 g, 1.0403 mmol) and 130 mL of water were

charged into a three-neck, 500 mL double jacketed reactor, equipped with a RTD temperature probe

and an overhead stirrer. The mixture was purged with nitrogen and stirred at 325 rpm for at least 30

min. Subsequently, the mixture was heated under inert atmosphere. When the temperature in the

reactor reached 70 °C, the addition of the MMA-CoBF solution started using a degassed syringe and a

syringe pump (feeding rate=0.666 mL/min, feeding time=30 min). When the addition was over,

stirring continued for another 30 min under the same conditions. Subsequently, the heat pump settings

were adjusted to 107 °C and stirring continued for 60 min enabling the reaction to stay at 80-82 °C.

2) PMMA-b-PBMA Diblock Copolymer Synthesis

In a typical chain extension aiming for DP=10 for the BMA block, 125 mL of PMMA

macromonomer latex were diluted by adding 37 mL of water to achieve a 10% solid content. The

resulting latex was charged in the reactor and purged with nitrogen for 30 min under stirring.

Subsequently, the emulsion was heated. When the temperature in the reactor reached 85-86 °C and

was stabilised, the simultaneous addition of BMA (15.9 mL, 14.22 g, 0.1 mol) and potassium

persulfate aqueous solution (79.53 mg potassium persulfate in 15.9 mL of water), both previously

degassed for 30 min started by the use of degassed syringes and a syringe pump (feeding rate=0.16




4

mL/min, feeding time=100 min). When the addition was over, stirring continued for another 60 min

under the same conditions.

For all the chain extension reactions the same process was followed, each time adjusting the monomer

and potassium persulfate aqueous solution quantities according to the desired degree of

polymerisation.

Section C. Tables and Figures

Supplementary Figure 1. 1H NMR trace of the of the PMMA macromonomer obtained via CCT in

emulsion polymerisation.




5

Supplementary Figure 2. MALDI spectra of the of the PMMA macromonomer obtained via CCT in

emulsion polymerisation.

1000 2000 3000 40000

2000

4000

6000

8000

10000

12000

14000

16000

18000

Inte

nsity

m/z

1200 1250 1300 13500

2000

4000

6000

8000

10000

12000

14000

16000

Inte

nsity

m/z

Observed mass [Na+]: 1223.6Expected mass [Na+]: 1223.6

100




6

Supplementary Figure 3. Proposed mechanisms of CCTP and addition-fragmentation reaction. 1, 2




7

Supplementary Figure 4. Typical set up for the synthesis of macromonomers or multiblock

copolymers employing a double jacketed reactor and securing a constant monomer addition rate by

the use of a syringe pump.

Supplementary Table 1. Experimental conditions used for the preparation of the tetracosablock

BMA homopolymer in emulsion at 85 °C with potassium persulfate as initiator

Entry Cycle M DP targeted

mmonomer

added (g) MCTA

added (g)

mKPS

added (mg)

VH2O

added (mL)

Vtotal (mL)[a]

S.C. (g/mL)

% wt solids

1 2 BMA 10 14.220 18 79.53 15.906 177.906 0.181 15.33 2 3 BMA 10 13.915 31.315 77.82 15.565 188.471 0.240 19.35 3 4 BMA 10 13.611 44.03 76.13 15.225 198.696 0.290 22.48 4 5 BMA 10 13.317 56.191 74.48 14.896 208.592 0.333 24.99 5 6 BMA 10 13.036 67.843 72.91 14.582 218.174 0.371 27.04 6 7b BMA 10 4.117 25.48 23.03 4.605 233.925 0.126 11.23 7 8 BMA 10 4.038 28.967 22.58 4.517 233.442 0.141 12.39 8 9 BMA 10 3.959 32.3 22.14 4.428 232.87 0.156 13.47 9 10 BMA 10 3.881 35.479 21.71 4.341 232.211 0.169 14.49

10 11 BMA 10 3.803 38.515 21.27 4.254 231.465 0.183 15.46 11 12 BMA 10 3.726 41.403 20.84 4.168 230.633 0.196 16.36 12 13c BMA 10 2.827 34.2 15.81 3.162 310.962 0.119 10.64 13 14 BMA 10 2.785 36.432 15.57 3.115 309.077 0.127 11.26




8

14 15 BMA 10 2.743 38.582 15.34 3.068 307.145 0.134 11.86 15 16 BMA 10 2.701 40.655 15.11 3.021 305.166 0.142 12.44 16 17 BMA 10 2.659 42.646 14.87 2.974 303.140 0.149 12.99 17 18 BMA 10 2.618 44.560 14.64 2.928 301.068 0.157 13.55 18 19d BMA 10 1.688 30.400 9.44 1.888 275.488 0.116 10.43 19 20 BMA 10 1.659 31.508 9.28 1.856 272.344 0.122 10.86 20 21 BMA 10 1.630 32.557 9.12 1.823 269.167 0.127 11.27 21 22 BMA 10 1.601 33.552 8.95 1.791 265.958 0.132 11.67 22 23 BMA 10 1.572 34.493 8.79 1.758 262.716 0.137 12.07 23 24 BMA 10 1.543 35.380 8.63 1.726 259.442 0.142 12.46

[a]: after the end of each cycle, a sample of 5 mL was taken. The amount of CTA removed from the system was taken into account for the calculations of the next cycle

[b]: 70 mL of the latex of cycle 6 were diluted to 10 % wt of solids by adding 159.32 mL of H20

[c]: 180 mL of the latex of cycle 12 were diluted to 10 % wt of solids by adding 127.8 mL of H20

[d]: 200 mL of the latex of cycle 18 were diluted to 10 % wt of solids by adding 73.6 mL of H20

Supplementary Table 2. Characterisation data for the synthesis of the tetracosablock BMA

homopolymer in emulsion at 85 °C with potassium persulfate as initiator

Entry Cycle Conv.a (%)

Mn,th (g/mol)

Mn,SEC (g/mol) ÐSEC Sizeb

(nm) ÐDLS

1 CTA >99 1,800 2,000 1.7 166 0.072 2 1 >99 3,200 3,500 1.3 190 0.041 3 2 >99 4,600 4,600 1.25 200 0.073 4 3 >99 6,000 6,100 1.16 209 0.067 5 4 >99 7,400 7,300 1.15 213 0.096 6 5 >99 8,800 9,000 1.14 220 0.091 7 6 >99 10,200 10,400 1.10 232 0.096 8 7 >99 11,600 11,600 1.11 244 0.110 9 8 >99 13,000 12,600 1.11 250 0.109 10 9 >99 14,400 13,900 1.12 258 0.118 11 10 >99 15,800 15,000 1.12 265 0.137 12 11 >99 17,200 16,000 1.12 279 0.131 13 12 >99 18,600 17,500 1.12 285 0.103 14 13 >99 20,000 18,500 1.12 289 0.111 15 14 >99 21,400 20,100 1.12 296 0.105 16 15 >99 22,800 21,500 1.14 302 0.123 17 16 >99 24,200 23,000 1.15 309 0.109 18 17 >99 25,600 24,400 1.16 315 0.106 19 18 >99 27,000 25,400 1.16 320 0.117 20 19 >99 28,400 26,800 1.18 325 0.089 21 20 >99 29,800 27,800 1.18 329 0.117 22 21 >99 31,200 28,800 1.18 334 0.109




9

23 22 >99 32,600 29,800 1.19 341 0.112 24 23 >99 34,000 30,700 1.21 347 0.120

Supplementary Figure 5. SEC traces of the of the tetracosablock BMA homopolymer.

Supplementary Figure 6. 1H NMR traces of the of the tetracosablock BMA homopolymer.

100 1000 10000 1000000.0

0.5

1.0

wdlo

gM

M (g/mol)

6 5 4 3 2 1 0

>99%>99%

>99%>99%

>99%>99%

>99%

>99%>99%

>99%>99%

>99%>99%

>99%>99%

>99%>99%>99%

>99%

>99%>99%

>99%>99%

>99%

2122

20

2423

1416

1715

1819

131211

910

876

5432

1

>99%

(ppm)




10

Supplementary Figure 7. Evolution of the hydrodynamic diameter of the tetracosablock BMA

homopolymer, as obtained by Z-average measurements, along with the corresponding number-

average molecular weight values.

Supplementary Figure 8. a) Evolution of theoretical (black straight line) and experimental molecular weight Mn (▲) and Mw ( ) determined by SEC b) Mw/Mn (●) versus the number of cycles during

synthesis of tetracosablock homopolymer.

0 5000 10000 15000 20000 25000 30000 35000150

200

250

300

350

400

450

Hyd

rody

nam

ic D

iam

eter

(nm

)

M (g/mol)

0

10000

20000

30000

40000

Mw

/Mn

M (g

/mol

)

0 5 10 15 20 25

1.0

1.5

2.0

Number of cycles

CTA

(a)

(b)




11

Supplementary Figure 9. 1H NMR traces of the of the PMMA macromonomer obtained via CCT in

emulsion polymerisation and the residual MMA monomer.

Supplementary Table 3. Experimental conditions used for the preparation of the tetracosablock

copolymer in emulsion at 85 °C with potassium persulfate as initiator

Entry Cycle Monomer

DP targeted

M monomer

added (g)

MCTA

added (g)

mKPS

added (mg)

VH2O

added (mL)

Vtotal (mL)[a]

S.C. (g/mL)

% wt solids

1 2 BMA 10 12.798 18 71.57 14.315 176.315 0.175 14.87 2 3 BzMA 10 15.978 29.923 76.82 15.364 186.679 0.246 19.74 3 4b EHMA 10 5.548 14.4 31.34 6.269 135.869 0.147 12.80 4 5 BMA 10 3.795 19.213 21.22 4.245 135.114 0.170 14.55 5 6 BzMA 10 4.678 22.158 22.48 4.497 134.611 0.199 16.62 6 7c EHMA 10 2.066 10.725 11.67 2.335 98.86 0.129 11.46 7 8 BMA 10 1.393 12.146 7.79 1.558 95.418 0.142 12.43 8 9 BzMA 10 1.689 12.829 8.12 1.624 92.042 0.158 13.62 9 10d EHMA 10 1.393 10.85 7.87 1.574 99.224 0.123 10.98

10 11 BMA 10 0.939 11.628 5.25 1.050 95.274 0.132 11.65 11 12 BzMA 10 1.137 11.907 5.47 1.094 91.368 0.143 12.49 12 13 EHMA 10 1.187 12.329 6.71 1.342 87.71 0.154 13.35 13 14 BMA 10 0.795 12.746 4.44 0.889 83.599 0.162 13.94 14 15 BzMA 10 0.955 12.731 4.59 0.918 79.517 0.172 14.68 15 16e EHMA 10 0.901 11.69 5.09 1.018 106.228 0.119 10.59 16 17 BMA 10 0.609 11.996 3.41 0.681 101.909 0.124 11.01 17 18 BzMA 10 0.739 11.985 3.55 0.711 97.620 0.130 11.53 18 19 EHMA 10 0.775 12.074 4.38 0.876 93.496 0.137 12.08 19 20 BMA 10 0.521 12.164 2.92 0.583 89.079 0.142 12.47 20 21 BzMA 10 0.628 11.975 3.03 0.605 84.684 0.149 12.95 21 22f EHMA 10 0.563 10.22 3.18 0.635 92.615 0.116 10.43 22 23 BMA 10 0.378 10.203 2.12 0.423 88.038 0.120 10.73 23 24 BzMA 10 0.472 10.341 2.27 0.453 86.491 0.125 11.11

6.0 5.8 5.6 5.4 5.2 5.0

(ppm)6.0 5.8 5.6 5.4 5.2 5.0

(ppm)6.0 5.8 5.6 5.4 5.2 5.0

(ppm)

6.0 5.8 5.6 5.4 5.2 5.0

(ppm)

a

cd

b

CTA Monomer




12





[e]: 70 mL of the latex of cycle 15 were diluted to 10 % wt of solids by adding 35.21 mL of H20

[f]: 70 mL of the latex of cycle 21 were diluted to 10 % wt of solids by adding 21.98 mL of H20

Supplementary Table 4. Characterisation data for the synthesis of the tetracosablock copolymer in

emulsion at 85 °C with potassium persulfate as initiator


Mn,th

(g/mol) Mn,SEC

(g/mol) ÐSEC Sizeb (nm) ÐDLS

1 CTA >99 2,000 2,000 1.61 165 0.049 2 1 98 3,400 3,700 1.28 188 0.034 3 2 99 5,200 5,300 1.17 198 0.074 4 3 >99 7,200 6,600 1.13 204 0.060 5 4 99 8,600 7,700 1.12 210 0.030 6 5 99 10,400 9,000 1.11 214 0.066 7 6 >99 12,400 10,100 1.10 223 0.089 8 7 >99 13,800 11,100 1.10 234 0.102 9 8 98 15,600 12,700 1.11 243 0.076

10 9 >99 17,600 13,800 1.12 263 0.137 11 10 98 19,000 14,700 1.13 271 0.136 12 11 99 20,800 16,100 1.15 280 0.099 13 12 >99 22,800 17,400 1.16 286 0.093 14 13 >99 24,200 18,400 1.18 292 0.135 15 14 >99 26,000 20,500 1.20 300 0.127 16 15 >99 28,000 21,200 1.24 304 0.099 17 16 98 29,400 22,700 1.24 313 0.126 18 17 >99 31,200 24,100 1.27 331 0.130 19 18 >99 33,200 25,800 1.32 341 0.116 20 19 >99 34,600 28,100 1.34 353 0.139 21 20 >99 36,400 29,500 1.35 360 0.112 22 21 >99 38,400 30,500 1.43 365 0.064 23 22 >99 39,800 31,800 1.45 373 0.135 24 23 >99 41,600 33,700 1.46 380 0.140




13

Supplementary Figure 10. Evolution of the hydrodynamic diameter of the tetracosablock copolymer

blocks, as obtained by Z-average measurements, along with their corresponding number-average

molecular weight.

Supplementary Figure 11. 1H NMR traces of the of the tetracosablock copolymer blocks.

0 5000 10000 15000 20000 25000 30000 35000150

200

250

300

350

400

Hyd

rody

nam

ic D

iam

eter

(nm

)

M (g/mol)

6 5 4 3 2 1 0

>99%>99%

>99%>99%

>99%99%>99%>99%

>99%>99%

>99%

99%99%

99%

99%99%

99%99%

98%

>99%

>99%>99%

>99%

>99%

>99%20

2122

2423

1816

19

121314

10

15

11

17

98

4

75

6

23

1

>99%

(ppm)




14

Supplementary Figure 12. SEC traces of the of the tetracosablock copolymer blocks.

Supplementary Figure 13. Dispersity (Ð) as a function of the number of cycles for the

tetracosablock copolymer

100 1000 10000 100000 10000000.0

0.5

1.0

wdl

ogM

M (g/mol)

0 5 10 15 20 25

1.1

1.2

1.3

1.4

1.5

1.6

1.7

Mw/M

n

Number of cycles




15

Supplementary Table 5. Experimental conditions used for the preparation of the heptablock


Entry Cycle M DP mmonomer

added (g)

MCTA

added

(g)

mKPS

added (mg)

VH2O

added (mL)

Vtotal (mL)[a]

S.C. (g/mL)

% wt solids

1 2b BMA 45 50.122 14.1 280.32 56.065 226.065 0.284 22.12 2 3c BzMA 45 27.295 27.4 131.22 26.245 272.845 0.200 16.69 3 4d EHMA 45 16.038 28.65 90.61 18.123 275.973 0.162 13.94 4 5 BMA 45 11.230 43.878 62.81 12.562 283.535 0.194 16.27 5 6 BzMA 45 14.084 54.138 67.71 13.542 292.077 0.234 18.93 6 7 EHMA 45 15.379 67.052 86.89 17.378 304.455 0.271 21.31


[b]: 100 mL of the latex of cycle 1 were diluted by adding 70 mL of H20

[c]: 100 mL of the latex of cycle 2 were diluted by adding 146.6 mL of H20


Supplementary Table 6. Characterisation data for the synthesis of the heptablock copolymer in



Mn,th

(g/mol) Mn,SEC


1 CTA 100 1,800 2,400 1.52 169 0.042 2 1 100 8,200 7,600 1.08 218 0.086 3 2 99 16,100 16,100 1.10 270 0.124 4 3 100 25,000 22,200 1.13 324 0.112 5 4 99 31,400 27,600 1.15 340 0.133 6 5 >99 39,300 33,900 1.21 365 0.136 7 6 98 48,200 41,300 1.24 399 0.125




16

Supplementary Figure 14. 1H NMR traces of the of the heptablock copolymer blocks.

Supplementary Figure 15. Evolution of the hydrodynamic diameter of the heptablock copolymer


molecular weight.

6 5 4 3 2 1 0

99%

99%100%

100%

99%

100%

45

76

23

1

>99%

(ppm)

0 10000 20000 30000 40000150

200

250

300

350

400

450

Hyd

rody

nam

ic D

iam

eter

(nm

)

M (g/mol)




17

Supplementary Table 7. Experimental conditions used for the preparation of the undecablock


Cycle Monomer DP targeted

mmonomer

added (g)

MCTA

added

(g)

mKPS

added (mg)

VH2O

added (mL)

Vtotal (mL)[a]

S.C. (g/mL)

% wt solids

2 BMA 5 6.399 18 35.79 7.158 169.158 0.144 12.61 3 BzMA 10 15.937 23.679 76.62 15.324 179.482 0.221 18.08 4 EHMA 15 25.718 38.511 145.3 29.060 203.542 0.316 23.99 5b BMA 20 6.962 18.36 38.93 7.787 173.027 0.146 12.77 6 EHMA 25 11.959 24.592 67.56 13.513 181.54 0.201 16.76 7 EHMA 30 13.963 35.546 78.89 15.778 192.318 0.257 20.47 8 BzMA 35 14.468 48.224 69.55 13.911 201.229 0.312 23.75 9c BzMA 40 4.073 15.35 19.58 3.916 142.066 0.137 12.03 10 BMA 45 3.486 18.738 19.49 3.899 140.965 0.158 13.62 11 BMA 50 3.735 21.434 20.89 4.178 140.143 0.179 15.23




Supplementary Table 8. Characterisation data for the synthesis of the undecablock copolymer in



Mn,th

(g/mol) Mn,SEC


1 CTA >99 2,000 2,300 1.65 174 0.128 2 1 98 2,700 3,500 1.27 189 0.051 3 2 99 4,500 5,900 1.13 204 0.072 4 3 99 7,500 8,500 1.09 221 0.070 5 4 >99 10,800 11,000 1.08 248 0.135 6 5 >99 15,800 14,800 1.07 276 0.095 7 6 >99 21,700 18,500 1.09 315 0.148 8 7 100 27,900 23,200 1.12 327 0.144 9 8 100 30,600 29,300 1.17 362 0.096 10 9 >99 37,000 34,700 1.18 436 0.296 11 10 >99 44,100 42,000 1.25 453 0.250




18

Supplementary Figure 16. Dispersity (Ð) as a function of the number of cycles for the undecablock

copolymer

Supplementary Figure 17. Evolution of the hydrodynamic diameter of the undecablock copolymer


molecular weight.

Supplementary references

1. Suddaby, K. G., Haddleton, D. M., Hastings J. J., Richards S. N. & O'Donnell J. P. Catalytic Chain Transfer for Molecular Weight Control in the Emulsion Polymerization of Methyl Methacrylate and Methyl Methacrylate-Styrene. Macromolecules 29, 8083–8091 (1996).

0 2 4 6 8 10 121.0

1.1

1.2

1.3

1.4

1.5

1.6

1.7

Mw/M

n

Number of cycles

0 10000 20000 30000 40000 50000

200

300

400

500

600

Hyd

rody

nam

ic D

iam

eter

(nm

)

M (g/mol)




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2. Krstina, J. et al. Narrow Polydispersity Block Copolymers by Free-Radical Polymerization in the Presence of Macromonomers. Macromolecules 28, 5381-5385 (1995).


Documents

Sequence controlled methacrylic multiblock Sequence ......Instrumentation. 1H NMR spectra were recorded on Bruker DPX-300 and HD-400 spectrometers using a mixture of deuterated chloroform