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![Page 1: Thermoplastic Elastomers with Complex Macromolecular Architectures 179 Technical Meeting, April 18-20,2011, Akron, OH Nikos Hadjichristidis, University.](https://reader036.fdocuments.in/reader036/viewer/2022062423/56649e9e5503460f94b9f8b1/html5/thumbnails/1.jpg)
Thermoplastic Elastomers with Complex Macromolecular Architectures
179 Technical Meeting, April 18-20,2011, Akron, OH
Nikos Hadjichristidis, University of Athens, Greece
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Acknowledgements
Professor Jimmy Mays, University of Tennessee at Knoxville, USA
Assoc. 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
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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
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Non-Linear Block Copolymers
Ab (n: 2,3,5,7,11,17)n
Exact GraftDouble Graft
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
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a a
a
Si
CH3b
a cSi
CH3
aaa 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
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Block-Comb Copolymers
Block-Graft Copolymers
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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)
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Synthesis ofBlock-Double-Graft Co- and Terpolymers
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Monitoring the synthesis of
the BDG polymers by SEC
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Molecular Characteristics of Block-Double-Graft Terpolymers
BDG5
BDG6, BDG7, HDGBDG1 to BDG4
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Morphological Characteristics of Block-Double-Graft Terpolymers
BDG5
BDG6, BDG7, HDGBDG1 to BDG4
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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
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BDG5
SAXS
Totally disorder stateχN ~ 3Asymmetric : 11 vol % PBd-1,2
2nd Group
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3rd GroupTEM
SAXS
BDG6, BDG7, HDG
Symmetric: ~ 50 vol % (total PDs)
BDG7 similar
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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
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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)
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Synthesis of PS-PIIx-PS Copolymers
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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
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Molecular Characteristics of the PS-PIIx-PS Copolymers
Sample
PS 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
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Synthesis of PSS5-PII
x-PSS5 Copolymers
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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. PSS
5-PII10-PSS
5
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Molecular Characteristics of PSS5-PII
x-PSS5 Copolymers
Sample
PSS 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
branchesMw
a (x10-3) I b
2.66 1.07 5 26.8 1.12
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Synthesis of PS-PISIx-PS Copolymers
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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
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Molecular Characteristics PS-PISIx-PS Copolymers
Sample
PS 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
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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 matrix
PSS5-PII
10 0.19 66.0 62.8 PS cylinders in PI matrix
PSS5-PII
20 0.22 78 76.2 PS cylinders in PI matrix
PSS5-PII
10-PSS5 0.18 131 125 PS cylinders in PI matrix
PSS5-PII
20-PSS5 0.19 122 116 PS cylinders in PI matrix
PS-PISI2 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
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PSS5-PII
5 (φPS= 0.18)
PSS5-PII
10-PSS5 (φPS= 0.18)
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Stress-Strain Behavior of Block-Comb/Graft CopolymersInfluence of the Architecture
Kraton D1101
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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