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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

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slide1

Thermoplastic Elastomers with Complex Macromolecular Architectures

179 Technical Meeting, April 18-20,2011, Akron, OH

Nikos Hadjichristidis, University of Athens, Greece

slide2

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 ErmisIatrou, University of Athens, Greece
  • Assoc. professor MarinosPitsikalis ,University of Athens, Greece
  • Dr George Koutalas, University of Athens, Greece
  • Dr Gabriel Velis, University of Athens, Greece
  • Many Thanks to the Rubber Division of ACS
  • Special Thanks to Professor Roderic Quirk
slide3

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

slide4

Synthesis and Properties of Well-Defined Non-Linear Homo(rheology) and Block Copolymers (morphology and micellization)

Multiarm Stars

MMP

Dendritic Polymers

wdLDPE

Dumbell

Dendritic BC

Monomers: St, Bd, Is, 2VP, MMA, HIC, D3, NCAs

PBocLL-PBLG-PBocLL

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)

slide5

Dendritic G2 (or Star),G3 Combs

Dendritic Polymers G2, G3

Stars

wd-PE (Models)

α,ω-Branched

r-Combs

wd-LDPE (Models)

wd-LDPE (Models)

LDPE: Tree-like. High MW and Structural Dispersity

Exact Combs

MODEL POLYETHYLENES (Complex MA)

Low MW and Structural Dispersity

Understand the Behavior and Improve the Performance

slide6

Block-Graft Copolymers

Block-Comb Copolymers

slide7

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)

slide9

Monitoring the synthesis of

the BDG polymers by SEC

slide11

Morphological Characteristics of Block-Double-Graft Terpolymers

BDG1 to BDG4

BDG6, BDG7, HDG

BDG5

slide12

BDG1 similar to BDG3

1st Group

TEM

SAXS

χN (BDG1-BDG3): 1.1-0.53); BDG4: 0.27

PBd-1,4/PBd-1,2: One Phase

BDG1 to BDG4

slide13

2nd Group

SAXS

Totally disorder state

χN ~ 3

Asymmetric : 11 vol % PBd-1,2

BDG5

slide14

3rd Group

TEM

BDG7 similar

SAXS

Symmetric: ~ 50 vol % (total PDs)

BDG6, BDG7, HDG

slide15

Stress-strain curves for (1) BDG6, 9 junction points, branch mol.weight 14 000 g/mol; (2) BDG7, 3 junction points, branch molecular weight32 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 weight13 000 g/mol.

BDG6, BDG7, HDG

block comb graft copolymers

PS-PIIx-PS

PSS5-PIIx-PSS5

PS-PISIx-PS

Block-Comb/Graft Copolymers

Macromolecules, 38, 4996 (2005); 40, 5835 (2007);

J. Polym. Sci., Polym. Chem., 43, 4030 (2005); 43, 4040 (2005)

KGK-KautschukGummiKunststoffe, 61, 597 (2008)

monitoring the synthesis of ps pi i 10 ps by sec
Monitoring the Synthesis of PS-PII10-PS by SEC

PI macromonomer

PI branch

PS block

PS-PII5copolymer

PS-b-(PI-g-PI)-b-PS

Fract. PS-b-(PI-g-PI)-b-PS

molecular characteristics of the ps pi i x ps copolymers
Molecular Characteristics of thePS-PIIx-PS Copolymers

a: SEC-TALLS inTHFat 35οC; b: SEC inTHF at 35οC;

c: Membrane Osmometry in toluene at 40οC; d: Calculated fromMw and Mn,

e: 1H NMR inCDCl3 at 30οC

monitoring the synthesis of ps s 5 pi i 10 ps s 5
Monitoring the Synthesis of PSS5-PII10-PSS5

PS branch

PS macromon.

PSS block

(PS-g-PS)-b-(PI-b-PI)

PI branch

PI macromon.

Fraction. PSS5-PII10-PSS5

(PS-g-PS)-b-(PI-b-PI)-b-(PS-g-PS)

molecular characteristics of ps s 5 pi i x ps s 5 copolymers
Molecular Characteristics ofPSS5-PIIx-PSS5 Copolymers

a: SEC-TALLS inTHFat 35οC; b: SEC inTHF at 35οC;

c: Membrane Osmometry in toluene at 40οC; d: Calculated from Mw and Mn;

e: 1H NMR inCDCl3at 30οC

monitoring the synthesis of ps pi s i 4 ps by sec
Monitoring the Synthesis of PS-PISI4-PS by SEC

PS-b-PI arm

PS-b-PI macromon.

PS arm block

PS block of the bb

PS-b-[PI-g-(PI-b-PS)]-b-PS

PS-b-[PI-g-(PI-b-PS)]

PS-b-[PI-g-(PI-b-PS)]-b-PS

Fractionated

molecular characteristics ps pi si x ps copolymers
Molecular CharacteristicsPS-PISIx-PS Copolymers

a: SEC-TALLS inTHFat 35οC; b: SEC inTHF at 35οC;

c: Membrane Osmometry in toluene at 40οC; d: Calculated fromMw and Mn;e: 1H NMR inCDCl3at 30οC

results
ΤΕΜ Results

χSI= 0.074 at 120οC

ρPS= 1.05 g/cm3 at 120οC

ρPI= 0.91 g/cm3 at 120οC

slide27

PSS5-PII5 (φPS= 0.18)

PSS5-PII10-PSS5 (φPS= 0.18)

slide28

Stress-Strain Behavior of Block-Comb/Graft Copolymers

Influence of the Architecture

Kraton D1101

slide29

Conclusions

  • Anionic 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