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Block Copolymers
(FORTH / University of Athens)


Molecular Characteristics Of Triblock Tripolymers Of Styrene, Isoprene And Dimethylsiloxane
(PS-b-PI-b-PDMS)
Polymer Mna
(PS)
.10-3		 Mna
(PS-PI)
.10-3		 Mna
(PS-PI-PDMS)
.10-3		 Mw/Mnb %
PSc
w/w		 %
PIc
w/w		 %
PDMSc
w/w		 Quantity
(g)
S45I41D19d 45,0 85,7 104,9 1,02 43,5 37,8 18,7 2
S57I70D23 57,1 127,4 150,9 1,06 39,3 45,7 15,0 0.5
S81I29D18 80,6 109,1 127,5 1,04 63,9 22,4 13,7 0.5
S20I60D32 20,5 80,6 112,7 1,04 18,4 53,5 28,1 0.5
S48I18D54 48,0 66,1 119,7 1,05 39,3 15,5 45,2 10
S19I61D51 19,2 80,5 131,3 1,03 14,9 47,1 38,0 6
S79I35D23 78,7 113,2 136,2 1,06 58,2 24,7 17,1 12
S60I59D60 60,5 119,0 178,9 1,05 33,5 33,1 33,4 8
S60I20D60 60,2 80,6 141,1 1,04 43,0 15,2 41,8 2

a Membrane osmometry in toluene at 35 șC
b SEC
c 1H NMR in CDCl3
d S (Styrene), I (Isoprene), D (Dimethylsiloxane)		 PS-PI-PDMS

bookFragouli PG, Iatrou H, Hadjichristidis N J. Polym. Science, Part A: Polym. Chem. 2004, 42 (3), 514
Synthesis and characterization of linear tetrablock quarterpolymers of styrene, isoprene, dimethylsiloxane, and 2-vinylpyridine


Molecular Characteristics Of Linear Tetrablock Quarterpolymers Of Styrene, Isoprene, Dimethylsiloxane And 2-Vinylpyridine
(PS-b-PI-b-PDMS-b-P2VP)
Polymer Mna
(PS)
.10-3		 Mna
(PS-PI)
.10-3		 Mna
(PS-PI-PDMS)
.10-3		 Mna
(PS-PI-
PDMS-P2VP)
.10-3		 Mw/Mnb %
PSc
w/w		 %
PIc
w/w		 %
PDMSc
w/w		 %
P2VPc
w/w		 g
S45I41D19V12 45,0 85,7 104,9 117,4 1,03 41,0 31,5 14,8 12,7 2
S57I70D23V26 57,1 127,4 150,9 176,6 1,07 37,3 38,9 11,4 12,4 5
S81I29D18V28 80,6 109,1 127,5 155,4 1,04 56,6 21,7 8,0 13,7 1
S81I29D18V38 80,6 109,1 127,5 165,7 1,05 45,1 15,3 14,2 25,4 2
S20I60D32V45 20,5 80,6 112,7 158,1 1,04 13,6 38,8 16,1 31,5 8
S30I25D18V26 30,1 54,9 72,9 98,8 1,03 30,0 25,5 25,3 21,1 2

a Membrane osmometry in toluene at 35 șC
b SEC

c 1H NMR in CDCl3
d S (Styrene), I (Isoprene), D (Dimethylsiloxane), V (2-vinylpyridine)

bookFragouli PG, Iatrou H, Hadjichristidis N J. Polym. Science, Part A: Polym. Chem. 2004, 42 (3), 514
Synthesis and characterization of linear tetrablock quarterpolymers of styrene, isoprene, dimethylsiloxane, and 2-vinylpyridine



Molecular Characteristics Of Linear Pentablock Quintopolymers Of Styrene, Isoprene, Dimethylsiloxane, 2-Vinylpyridine And Tert-Butyl Methacrylate
(PS-b-PI-b-PDMS-b-P2VP-b-P(t-BuMA))
Polymer Mna
(PS)
.10-3		 Mna
(PS-PI)
.10-3		 Mna
(PS-PI-PDMS)
.10-3		 Mna
(PS-PI-PDMS-
P2VP-P(t-BuMA))
.10-3		 %
PSa
w/w		 %
PIa
w/w		 %
PDMSa
w/w		 %
P2VPa
w/w		 %
P(tBuMA)a
w/w		 Ia g
S33I14D27V47M40b 33,3 47,5 74,4 161,4 20,6 8,8 16,7 29,1 24,8 1,05 2

a SEC (theoretical molecular weights)
b S (Styrene), I (Isoprene), D (Dimethylsiloxane), V (2-vinylpyridine), Μ (tert-butylmethacrylate)



Diblocks Containing PHIC
Polymer Ι Mn . 10-3 Quantity (g)
PS-PHIC(99-1%) 1.16 50 2.5
PS-PHIC(92-8%) 1.19 102 5.5
PS-PHIC(95-5%) 1.08 150 6
PS-PHIC(99-1%) 1.16 60 2.2
PS-PHIC(93-7%) 1.29 145 3.5
PI-PHIC(30-70%) 1.25 82 1.5

bookZorba G., Vazaios A., Pitsikalis M., Hadjichristidis N., J. Polym. Science, Part A: Polym. Chem. 2005, 43 (16): 3533
Anionic polymerization of n-hexyl isocyanate with monofuctional initiators. Synthesis of well-defined diblock copolymers with styrene and isoprene



Molecular Characteristics Of Styrene - Isoprene Diblocks
Polymer Mn copol . 10-4 Mn PS. 10-3 Mw / Mn % wt PS Quantity (g)
SI – 40B 5.19 2.13 1.04 40 4
SI – 40 5.36 2.58 1.04 48 4
SI – 45 5.39 2.68 1.04 52 4
SI – 50 5.47 2.95 1.04 56 4
SI – 55 5.15 3.22 1.03 62 4
SI - 60 5.36 3.65 1.03 69 4



Molecular Characteristics Of Styrene - Isoprene Diblock Copolymers
Polymer Mw . 10-3 Mn . 10-3 I % wt PS Quantity (g)
SI-18/25 19.5 17.3 1.05 24 6.3
SI-25/25 24.3 23.8 1.05 25 2.1
SI-25/75 30.1 28.4 1.05 73 4.4
SI-8/50 10.0 1.05 50 4.2
CSI-40K 48.7 45.1 1.05 55 1.6



PS-b-PtBMA
Polymer Mn . 10-3 (SEC) Mw / Mn Quantity (g)
PS-PtBMA - 1 149 1.08 1
PS-PtBMA - 2 47 1.06 6.7




PS-b-PI Samples
Polymer Mn(branch) .10-3 a Mn(diblock) .10-3 a Mw/ Mn % PS b Quantity (g)
PS-b-PI -1 8 14.4 1.03 55 4.3
PS-b-PI -2 2.4 4.4 1.06 55 3.7
PS-b-PI -3 2 3.5 1.08 56 4
PS-b-PI -4 1.5 2.7 1.11 55 4.8
PS-b-PI -5 8.6 15.7 1.04 55 11.1
a: VPO in toluene at 50șC
b: average from 1H-NMR and SEC/UV




PS-b-P2VP Diblocks And P2VP Homopolymers

Polymer Mw total . 10-3 (SEC) Mw/ Mn Quantity (g)
PS-P2VP - 1 18 1.16 6.7
PS-P2VP - 2* 10.3 1.16 4.9
PS-P2VP - 3* 33 1.19 8
PS-P2VP - 4 90 1.11 2.8
PS(d8) - P2VP 18 1.08 1.2
P2VP - 1 27.9 1.18 10.3
P2VP - 2 200 1.05 1.2

*They need fractionation




Star-Block

Polymer
(star copolymers)		 Mna. 10-3 Mnb. 10-3 Mwc. 10-3 dn / dcd I
(Mw/Mn)e		 % wt
PSf		 % wt
PSg		 Quantity (g)
PS-A 6.3 - - - 1.04 - - 0.6
PSPI-A - 14.0 14.5 0.159 1.03 46 45 0.2
4(SI)-A - 54.3 57.5 1.161 1.04 44 46 5.8
PS-B 13.3 - - - 1.03 - - 0.45
PSPI-B - 18.6 19.4 0.179 1.03 68 71 0.2
4(SI)-B - 70.5 72.2 0.180 1.03 68 71 8.6

a : VPO in toluene at 50șC
b : MO in toluene at 30șC
c : LALLS in THF at 25șC
d : in THF at 25șC
e : SEC in THF at 30șC
f : 1H-NMR
g : UV/SEC (254nm) in THF



Molecular Characteristics Of The Poly (tert butyl methacrylate-b-styrene-b-tert butylmethacrylate)
And The Hydrolyzed Poly (methacrylic acid-b-styrene-b-methacrylic acid)

Polymer Mw . 10-3 dn / dc I (Mw/Mn) % wt PS Quantity (g)
S-tBMA-3 34.7 0.121 1.06 34 0.2
S-MA-3 26.0 - - 48 0.5
S-tBMA-4 68.0 0.099 1.04 20 0.7
S-MA-4 46.5 - - 29 0.3
S-tBMA-5 108.5 0.114 1.05 32 2.1
S-MA-5 79.5 - - 44 0.8
S-tBMA-6 70.0 0.095 1.03 17 1.9
S-MA-6 47.0 - - 25 0.9
S-tBMA-7 136.0 0.098 1.04 18 0.3
S-MA-7 92.0 - - 27 0.6
tBMA-S-tBMA 72.3 0.084 1.04 7.5 11.7
MA-S-MA 45.9 - - 13


Polymer Mw . 10-3 I Quantity (g)
PMMA 50-350 1.1-1.3 30
Poly(n-butyl) MA (PnBuMA) 150-300 1.2-1.3 10
Poly(t-butyl) MA (PtBuMA) 200-400 1.2-1.3 10
Poly(n-hexyl) MA (PnHMA) 200 1.25 5
Poly(sec-butyl) MA (PsBuMA) 250 1.2 5
Poly(n-decyl) MA (PnDMA) 1800 1.3 5
Poly(stearyl) MA (PstMA) 280 1.35 5
Poly(trimethylsilyl) MA (PTMSiMA) 150 1.4 5


bookBatis C, Karanikolopoulos G, Pitsikalis M, Hadjichristidis N Macromolecules 2000, 33 (24), 8925

bookKaranikolopoulos G, Batis C, Pitsikalis M, Hadjichristidis N Macromolecules 2001, 34 (14), 4697



Polymer Mw . 10-3 I Quantity (g)
PMMA COM : PSt, PI, PSt-b-PI, PEO, P2MP
PMMA-co- PnDMA 200 1.4 5
PMMA-co- PstMA 150 1.35 5
PMMA-co- PtBuMA 80 2.0 5
PMMA-co- PsBuMA 100 1.6 5
PMMA-co- PTMSiMA 60 2.0 5
PMMA-co- PAllylMA 130 1.6 5
PMMA-co- PnHMA 170 1.3 5
PMMA-b- PcHMA 350 1.15 3
PMMA-b- PTMSiOEMA 450 1.2 3
PMMA--PSt 450 1.2 5
PMMA--PIs 400 1.2 7
PMMA--PEO 490 1.7 5
PMMA--P2MP 25 1.3 3
PMMA--(PSt-b-Is) 670 1.3 8
PPSt 45 1.05 2
PPIs 30 1.03 4
PnBuMA-b-PMMA 85-900 1.1-1.3 10


bookKaranikolopoulos G, Batis C, Pitsikalis M, Hadjichristidis N Journal of Polymer Science, Part A: Polym. Chem. 2004, 42 (15), 3761


book Batis C, Karanikolopoulos G, Pitsikalis M, Hadjichristidis N Macromolecules 2003, 36 (26), 9763


bookKaranikolopoulos G, Batis C, Pitsikalis M, Hadjichristidis N Macromol. Chem. and Physics 2003, 204 (5-6), 831




Diblock Copolymers PS-b-PBOS
Sample Mn . 10-3 Mw .10-3 I % wt BOS Quantity
BS -1 130 142 1.09 10 2
BS -2 53 58 1.10 50 3
BS -3 70 74 1.05 30 1
BS -4 30 32 1.08 30 5
BS -5 75 77 1.02 95 2

  • Gkogkas G., Pispas S, Hadjichristidis N. et al in press


Tetrablock Copolymers Of PS, PI

Sample TB 2 TB 3

a : Membrane Osmometry in toluene at 34șC
b : LALLS in THF at 25șC
c : SEC in THF at 30șC
d : dn/dc in THF at 25șC
Mn PSa . 10-3 36.1 20.0
Mn PS-PIa . 10-3 52.6 38.5
Mw PS-PIa . 10-3 b 54.5 39.6
Mw/Mn PS-PIc 1.04 1.03
% wt PS UV-SECc 65 48
1H NMR 68 51
Mn PIa .10-3 32.5 18.8
Mn PS-PIa .10-3 50.0 39.3
Mw PS-PIa .10-3 52.2 40.1
Mw/Mn PI-PSc 1.04 1.03
% wt PS UV-SECc 35 51
1H NMR 37 52
Mn totala .10-3 103 80.2
Mwtotala .10-3 106 82.9
Mw/Mn totalc 1.03 1.04
% wt PS UV-SECc 51 51
1H NMR 52 50
dn/dcd 51 51
Quantity (g) 6.1 1.8

  • Chrissopoulou K, Tselikas Y, Anastasiadis SH, Fytas G, Semenov AN, Fleischer G, Hadjichristidis N, Thomas EL Macromolecules 1999, 32 (15): 5115


Block-Double-Graft Copolymers And Terpolymers Of S, Bd, And I

Sample Branches Block-Double Graft
Mna . 10-3 Mw/Mn c Mna . 10-3 Mw/Mn c wt % PS 1H NMR wt % PS UV/SEC Quantity (g)
P[S-b-(1,2Bd-g-1,4Bd2)] -1 3.0 1.06 84.2 1.05 35 34 0.3
P[S-b-(1,2Bd-g-1,4Bd2)] -2 3.0 1.06 53.1 1.05 19 18 2.0
P[S-b-(1,2Bd-g-1,4Bd2)] -3 2.3b 1.07 84.2 1.05 32 31 2.3
P[S-b-(1,2Bd-g-S2)] 5.0 1.08 156.6 1.06 89 87 3.3
P[S-b-(1,2Bd-g-I2)] 13.2 1.04 287.5 1.05 11 12 3.0
P{S-b-[1,2Bd-g-(S-b-I)2]} -1 14.0 1.06 280.0 1.08 52 52 5.0
P{S-b-[1,2Bd-g-(S-b-I)2]} -2 32.8 1.04 1.06 48 1.7
P[1,2Bd-g-(S-b-I)2] 12.5 1.03 235 1.07 45 42 11.8


a : MO in toluene at 35șC
b : VPO in toluene at 50șC
c : SEC in THF at 30șC
  • Velis G, Hadjichristidis N Journal of Polymer Science, Part A: Polym. Chemistry 2000, 38 (7): 1136


Linear And Star Polymers Containing PDMS

Sample Mn (PS)a
. 10-3		 Mn (PI)a
.10-3		 Mn (PDMS)a
. 10-3		 Mn (total)a
. 10-3		 Ib Quantity
(g)
PS-b-PDMS 34.0 - - 48.7 1.03 1
PS-b-PDMS-b-PS 34.0 - - 96.1 1.04 3
(PS)2PDMS 15.9 - 16.1 47.7 1.03 1
(PS)3PDMS 6.7 - 13.3 33.3 1.03 2
(PS)(PI)(PDMS) 19.5 20.7 19.0 58.9 1.04 4
PS-b-PI-b-PDMS-b-P2VP 29.1 - - 107.4 1.04 4

  • Bellas V, Iatrou H, Hadjichristidis N Macromolecules 2000, 33 (19): 6993
  • Bellas V, Iatrou H, Pitsinos EN, Hadjichristidis N Macromolecules 2001, 34 (16): 5376
  • Takahashi K, Hasegawa H, Hashimoto T, Bellas V, Iatrou H, Hadjichristidis N Macromolecules 2002, 35 (13): 4859


Diblock Copolymers Of PS, PI

Sample Mn (MO) .10-3 Mw (LALLS) .10-3 I (SEC) %wt PS
(1H NMR)		 %wt PS
(UV/SEC)		 Quantity (g)
PS-20/1 19.0 --- 1.03 --- --- 0.5
Difunctional PS 51.0 --- 1.03 --- --- 0.5
DB-20/20 39.0 40.2 1.05 48 47 0.5
SH-20/20 266.0 282.0 1.07 60 60 0.8
PS-20/2 21.0 --- 1.04 --- --- 0.5
Difunctional PS 46.0 --- 1.03 --- --- 0.5
DB-20/30 51.4 53.5 1.05 42 40 0.5
SH-20/30 315.2 337.3 1.08 50 51 0.5


DB: diblock branch, SH: final copolymer
The numbers next to letters indicate the molecular weights of each block
* : Number 3 indicates the three diblock branches




Miktoarm Star Copolymers Of PS, PI And Their Branches

Sample Mn (MO)
. 10-3		 Mw (LALLS)
. 10-3		 I
(SEC)		 %wt PS
(1H NMR)		 %wt PS
(UV/SEC)		 Quantity (g)
PS-20/1 19.0 --- 1.03 --- --- 0.5
DB-20/20 39.0 40.2 1.05 48 47 0.5
3-DB-20/20 * 126.0 132.8 1.04 58 57 0.5
PS-20/2 21.0 --- 1.04 --- --- 0.5
DB-20/30 51.4 53.5 1.05 42 40 0.5
3-DB-20/30*
(PS(PIPS)3)		 185.0 193.2 1.05 48 45 3.0


DB: diblock branch, SH: final copolymer
The numbers next to letters indicate the molecular weights of each block
* : Number 3 indicates the three diblock branches

  • Cho D, Park S, Chang T, Avgeropoulos A, Hadjichristidis N European Polymer Journal 2003, 39 (11): 2155
    “Characterization of a 4-miktoarm star copolymer of the (PS-b-PI)(3) PS type by temperature gradient interaction chromatography”

Sample Mn (MO)
. 10-3		 Mw (LALLS)
. 10-3		 I
(SEC)		 %wt PS
(1H NMR)		 %wt PS
UV/SEC)		 Quantity (g)
PS-16 16.0 --- 1.04 --- --- 0.5
DB-16/16 31.0 32.3 1.03 50 48 1.0
2DB-16/16 78.2 82.1 1.04 60 60 0.5
PS-20/2 21.0 --- 1.04 --- --- 0.5
DB-20/30 51.4 53.5 1.05 42 40 0.5
2DB-20/30
(PS(PIPS)2)		 129.0 113.5 1.06 50 51 1.5


DB: diblock branch
2DB: final miktoarm star polymer with 2 diblock branches
The numbers next to letters indicate the molecular weights of each block




Diblock Copolymers Of PS, PI

Sample Mn (MO)
. 10-3		 Mw (LALLS)
. 10-3		 I
(SEC)		 %wt PS
(1H NMR)		 %wt PS
(UV/SEC)		 Quantity (g)
PS-20/1 19.0 --- 1.03 --- --- 0.5
DB-20/20 39.0 40.2 1.05 48 47 0.5
TB-20/20/20 59.8 62.2 1.04 68 66 0.9
PS-20/2 21.0 --- 1.04 --- --- 0.5
DB-20/30 51.4 53.5 1.05 42 40 0.5
TB-20/30/20 72.1 76.5 1.06 59 57 4.0
PS-14 13.3 14.1 1.05 --- --- 0.5
DB-14/24 37.4 39.6 1.04 34 33 0.5
TB-14/48/14 70.5 73.6 1.05 34 36 0.5


DB: diblock copolymer
TB: final triblock product
The numbers next to letters indicate the molecular weights of each block

Last modified: 17/02/2008