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Thermoplastic Elastomers with Complex Macromolecular Architectures . 179 Technical Meeting, April 18-20,2011, Akron, OH. Nikos Hadjichristidis , University of Athens, Greece. Acknowledgements Professor Jimmy Mays, University of Tennessee at Knoxville, USA - PowerPoint PPT Presentation
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Thermoplastic Elastomers with Complex Macromolecular Architectures
179 Technical Meeting, April 18-20,2011, Akron, OH
Nikos Hadjichristidis, University of Athens, Greece
AcknowledgementsProfessor Jimmy Mays, University of Tennessee at
Knoxville, USAAssoc. Professor Sam Gido, UMASS Amherst, USA
Professor Roland Weidisch, Martin-Luther University at Halle, Germany
Assoc. Professor Ermis Iatrou, University of Athens, Greece
Assoc. professor Marinos Pitsikalis ,University of Athens, Greece
Dr George Koutalas, University of Athens, GreeceDr Gabriel Velis, University of Athens, Greece
Many Thanks to the Rubber Division of ACS Special Thanks to Professor Roderic Quirk
STRENTH OF ANIONIC POLYMERIZATION
No Termination (Trully Living)Well-Defined polymers(Low Molecular, Structural, Compositional
Dispersity, Control of MW up to a Few Hundred Thousands)
Compatible with Dienes (Butadiene, Isoprene,2-Methyl-pentadiene)Control of Microstructure (1,2; 1,4; cis and trans, Polyolefins by H2)
Not a Method of Choice in Industry. Many Steps under inert and Clean Atmosphere, Time Consuming
Only if it is Necessary, e.g. KRATONS
Why is Important for Industrial Application?Model Polymers, Structure-Properties relationships
Non-Linear Block CopolymersAb (n: 2,3,5,7,11,17)n
Exact GraftDouble G raft
A (n: 2,4,6,8,16)nnB
Non-Linear Block Terpolymers
α,ω-Branched Block Copolymers
Comb and Graft Copolymers
Synthesis and Properties of Well-Defined Non-Linear Homo(rheology) and Block Copolymers (morphology and micellization)
Prog. Polym. Sci.,24, 875 (1999); Chem. Rev., 101, 3747 (2001)Prog. Polym. Sci.,30, 725 (2005); Adv. Polym. Sci., 189, 1 (2005), Chem. Rev., 109, 5528 (2009)
Monomers: St, Bd, Is, 2VP, MMA, HIC, D3,
NCAs
Multiarm Stars
Dumbell
Dendritic PolymerswdLDPE
Dendritic BC
MMP
PBocLL-PBLG-PBocLL
a a
a
Si
CH3b
a cSi
CH3
a aa a
Dendritic G2 (or Star),G3 Combs
Dendritic Polymers G2, G3
wd-LDPE (Models)wd-LDPE (Models)
α,ω-Branched
Stars
r-Combs
MODEL POLYETHYLENES (Complex MA)Low MW and Structural Dispersity
Understand the Behavior and Improve the Performance
wd-PE (Models)
LDPE: Tree-like. High MW and Structural Dispersity
Exact Combs
Block-Comb Copolymers
Block-Graft Copolymers
Block-Double-Graft Co- and Terpolymers
Macromolecules, 29, 7022 (1996); 31, 5690 (1998); 31, 6697 (1998); 31, 7659 (1998); 33, 2039 (2000); 34, 6333 (2001); 35, 5903 (2002);
41, 4565 (2008); 42, 4155 (2009)Eur. Polym. J., 44, 3790 (2008); 45, 2902 (2009)
Macromol. Symp., 215, 111 (2004); 233, 42 (2006)Polymer, 50, 6297 (2009)
Synthesis ofBlock-Double-Graft Co- and Terpolymers
Monitoring the synthesis of
the BDG polymers by SEC
Molecular Characteristics of Block-Double-Graft Terpolymers
BDG5
BDG6, BDG7, HDGBDG1 to BDG4
Morphological Characteristics of Block-Double-Graft Terpolymers
BDG5
BDG6, BDG7, HDGBDG1 to BDG4
SAXS
TEM
χN (BDG1-BDG3): 1.1-0.53); BDG4: 0.27
PBd-1,4/PBd-1,2: One Phase
BDG1 to BDG4
1st Group
BDG1 similar to BDG3
BDG5
SAXS
Totally disorder stateχN ~ 3Asymmetric : 11 vol % PBd-1,2
2nd Group
3rd GroupTEM
SAXS
BDG6, BDG7, HDG
Symmetric: ~ 50 vol % (total PDs)
BDG7 similar
Stress-strain curves for (1) BDG6, 9 junction points, branch mol. weight 14 000 g/mol; (2) BDG7, 3 junction points, branch molecular weight 32 800 g/mol; (3) HDG, 9 junction points, branch molecular weight 12 500 g/mol; (4) Kraton D1101; and (5) PI-g-PS2 multigraft copolymer with 9 junction points, branch molecular weight 13 000 g/mol.
BDG6, BDG7, HDG
Block-Comb/Graft Copolymers
PS-PIIx-PS
PSS5-PII
x-PSS5
PS-PISIx-PS
Macromolecules, 38, 4996 (2005); 40, 5835 (2007);J. Polym. Sci., Polym. Chem., 43, 4030 (2005); 43, 4040 (2005)
KGK-Kautschuk Gummi Kunststoffe, 61, 597 (2008)
Synthesis of PS-PIIx-PS Copolymers
Monitoring the Synthesis of PS-PII10-PS by SEC
PI branch PI macromonomerPS block
PS-PII5 copolymer PS-b-(PI-g-PI)-b-PS
Fract. PS-b-(PI-g-PI)-b-PS
Molecular Characteristics of the PS-PIIx-PS Copolymers
SamplePS block PI branch Final Copolymer
Mwa
(x10-3) I b Mwa (x10-
3) I b Mnc
(x10-3)Mw
a (x10-3) I b I d %wt PS
e
PS-PII5
21.5 1.03 2.36 1.06
69.2 73.0 1.03 1.05 19.1
PS-PII10 61.0 72.6 1.15 1.19 23.0
PS-PII20 55.0 70.0 1.26 1.27 22.4
PS-PII10-PS 140 145 1.05 1.04 19.2
PS-PII20-PS 122 132 1.07 1.08 23.0
PS-PII40-PS 111 122 1.07 1.10 22.4
a: SEC-TALLS in THF at 35 οC; b: SEC in THF at 35 οC;c: Membrane Osmometry in toluene at 40 οC; d: Calculated from Mw and Mn,
e: 1H NMR in CDCl3 at 30 οC
Synthesis of PSS5-PII
x-PSS5 Copolymers
Monitoring the Synthesis of PSS5-PII
10-PSS5
PS branch PS macromon. PSS block
PI branch PI macromon. (PS-g-PS)-b-(PI-b-PI)
(PS-g-PS)-b-(PI-b-PI)-b-(PS-g-PS) Fraction. PSS5-PII
10-PSS5
Molecular Characteristics of PSS5-PII
x-PSS5 Copolymers
SamplePSS block PI branch Final Copolymer
Mwa
(x10-3) I b Mwa
(x10-3) I b Mnc
(x10-3)Mw
a (x10-3) I b I d %wt
PS e
PSS5-PII
5
26.8 1.12 3.31 1.10
70.3 77 1.07 1.10 20.5
PSS5-PII
10 66.0 80 1.19 1.21 21.4
PSS5-PII
20 78 98 1.25 1.26 24.8
PSS5-PII
10- PSS5 131 143 1.07 1.09 20.5
PSS5-PII
20- PSS5 122 136 1.07 1.11 21.4
a: SEC-TALLS in THF at 35 οC; b: SEC in THF at 35 οC;c: Membrane Osmometry in toluene at 40 οC; d: Calculated from Mw and Mn;
e: 1H NMR in CDCl3 at 30 οC
PS branches PSS block
Mwa (x10-3) I b Number of
branches Mwa (x10-3) I b
2.66 1.07 5 26.8 1.12
Synthesis of PS-PISIx-PS Copolymers
Monitoring the Synthesis of PS-PISI4-PS by SEC
PS arm block PS-b-PI arm PS-b-PI macromon.
PS-b-[PI-g-(PI-b-PS)]
PS block of the bb
PS-b-[PI-g-(PI-b-PS)]-b-PSFractionated
PS-b-[PI-g-(PI-b-PS)]-b-PS
Molecular Characteristics PS-PISIx-PS Copolymers
SamplePS block PS arm PS-PI arm Final Copolymer
Mwa
(x10-3) I b Mwa
(x10-3) I b Mwa
(x10-3) I b Mnc
(x10-3)Mw
a (x10-6) I b I d %wt
PS e
PS-PISI2
21.5 1.03 12.0 1.03 20.2 1.04
145 0.157 1.07 1.09 27.0
PS-PISI4 - 1.27 1.06 - 33.6
PS-PISI4-PS - 0.307 1.07 - 26.2
a: SEC-TALLS in THF at 35 οC; b: SEC in THF at 35 οC;c: Membrane Osmometry in toluene at 40 οC; d: Calculated from Mw and Mn;
e: 1H NMR in CDCl3 at 30 οC
ΤΕΜ ResultsSample ΦPS Mn x 10-3 χΝ Morphology
PS-PII5 0.18 69.2 67.5 PS cylinders in PI matrix
PS-PII10 0.21 61.0 58.5 PS cylinders in PI matrix
PS-PII20 0.20 55.0 52.0 PS cylinders in PI matrix
PS-PII10-PS 0.18 140 137 PS cylinders in PI matrix
PS-PII20-PS 0.21 122 117 PS cylinders in PI matrix
PS-PII40-PS 0.20 111 105 PS cylinders in PI matrix
PSS5-PII
5 0.18 70.3 67.5 PS cylinders in PI matrixPSS
5-PII10 0.19 66.0 62.8 PS cylinders in PI matrix
PSS5-PII
20 0.22 78 76.2 PS cylinders in PI matrixPSS
5-PII10-PSS
5 0.18 131 125 PS cylinders in PI matrixPSS
5-PII20-PSS
5 0.19 122 116 PS cylinders in PI matrixPS-PISI
2 0.24 145 141 PS cylinders in PI matrix
χSI= 0.074 at 120 οC
ρPS= 1.05 g/cm3 at 120 οC
ρPI= 0.91 g/cm3 at 120 οC
PSS5-PII
5 (φPS= 0.18)
PSS5-PII
10-PSS5 (φPS= 0.18)
Stress-Strain Behavior of Block-Comb/Graft CopolymersInfluence of the Architecture
Kraton D1101
ConclusionsAnionic Polymerization High Vacuum Techniques
Lead to Well-Defined Thermoplastic Elastomers with
Complex Macromolecular Architectures
These Novel Thermoplastic Elastomers Show
Interesting Mechanical Properties
Strain at Break Can Greatly Exceed Those of
Commercial TPE
