Thermoplastic Elastomers with Complex Macromolecular Architectures 179 Technical Meeting, April 18-20,2011, Akron, OH Nikos Hadjichristidis, University

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

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

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 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

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

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

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

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. PSS

5-PII10-PSS

5

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;


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

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

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;


ΤΕΜ ResultsSample ΦPS Mn x 10-3 χΝ Morphology

PS-PII5 0.18 69.2 67.5 PS cylinders in PI matrix



PS-PII10-PS 0.18 140 137 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

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

Documents

Thermoplastic Elastomers with Complex Macromolecular Architectures 179 Technical Meeting, April 18-20,2011, Akron, OH Nikos Hadjichristidis, University