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Mechanochemistry of Topological Complex Polymer Systems

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Polymer Mechanochemistry

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 369))

Abstract

Although existing since the concept of macromolecules, polymer mechanochemistry is a burgeoning field which attracts great scientific interest in its ability to bias conventional reaction pathways and its potential to fabricate mechanoresponsive materials. We review here the effect of topology on the mechanical degradation of polymer chains and the activation of mechanophores in polymer backbones. The chapter focuses on both experimental and theoretical work carried out in the past 70 years. After a general introduction (Sect. 1), where the concept, the history, and the application of polymer mechanochemistry are briefly described, flow fields to study polymer mechanochemistry are discussed (Sect. 2), results of mechanochemistry study are presented for linear polymers (Sect. 3), cyclic polymers (Sect. 4), graft polymers (Sect. 5), star-shaped polymers (Sect. 6), hyperbranched polymers and dendrimers (Sect. 7), and systems with dynamic topology (Sect. 8). Here we focus on (1) experimental results involving the topological effect on the coil-to-stretch transition and the fracture of the polymer chains, (2) the underlying mechanisms and the key factor that determines the mechanical stability of the macromolecules, (3) theoretical models that relate to the experimental observations, and (4) rational design of mechanophores in complex topology to achieve multiple activations according to the existing results observed in chain degradation.

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Abbreviations

\( \dot{\varepsilon} \) :

Strain rate

\( {\dot{\varepsilon}}_{\mathrm{A}} \) :

Critical strain rate for mechanophore activation

\( {\dot{\varepsilon}}_{\mathrm{C}} \) :

Critical strain rate for CST

\( {\dot{\varepsilon}}_{\mathrm{F}} \) :

Critical strain rate for chain scission

[η]:

Intrinsic viscosity

ΔE*(0):

Activation energy at rest (zero force)

ΔE*(F):

Activation energy of a reaction as a function of external force

ΔP A :

Pressure drop with the drag reduction agent

ΔP S :

Pressure drop with pure solvent

Δζ :

Distance from reactant to transition-state configuration along the reaction coordinate ζ

ζ :

Reaction coordinate

η Base :

Kinematic viscosity of the base oil

η Fresh :

Kinematic viscosity of the fresh unsheared lubricant

η s :

Dynamic viscosity of the fluid

η Shear :

Kinematic viscosity of the sheared lubricant

ν :

Flory exponent

ξ :

Hydrodynamic drag coefficient

ξ g :

Hydrodynamic drag coefficient of grafted chains

ρ s :

Density of the solvent

σ F :

Critical force to break a bond

σ i :

Cumulative hydrodynamic drag force on each bead

σ mid :

Maximum hydrodynamic drag force at the midpoint of a linear chain

σ mid_g :

Additional hydrodynamic drag force from side chain

σ mid_graft :

Maximum hydrodynamic drag force at the midpoint of a backbone for grating polymers

τ 0 :

Longest relaxation time of a polymer chain

a :

Radius of the beads

b :

Length of chain segment

b g :

Distance between neighboring side chains

c :

Size of the bead in the side chain

d :

Hydraulic diameter of the pipe

DB:

Degree of branching

De :

Deborah number

DRE:

Drag reduction efficiency

f :

Hydrodynamic drag force on a bead

F :

External force exerts on a chemical reaction

f arm :

Number of arms in a star-shaped molecule

k :

Rate constant

k 0 :

Rate constant at zero force

k B :

Boltzmann constant

M :

Total molecular weight of a chain

M arm :

Molecular weight of an arm in a star-shape molecule

M lim :

Limiting molecular weight of a linear polymer chain to observe mechanical degradation

M span :

Molecular weight of a spanning path in a nonlinear macromolecule

M w :

Weight averaged molecular weight

N :

Total number of repeating units of a macromolecule

N arm :

Number of repeating units of an arm

N L :

Number of repeating unit of the linear backbone for grafting chain

N lad :

Maximum number of repeating unit permissible of a linear macromolecule in a ladder-like polymer

N lin :

Maximum number of repeating unit permissible of a linear macromolecule in isolated conformations

N span :

Number of repeating units along the spanning path

p :

Number of side chains in bead-rod model

R :

End-to-end distance of a polymer coil

R arm :

End-to-end distance of the arm

Re :

Reynolds number

R G :

Radius of gyration for a polymer coil

R H :

Hydrodynamic radius of a polymer coil

S 1 :

Shielding factor of the linear backbone

S 2 :

Shielding factor of the grafting chain

T :

Kelvin temperature

V :

Mean velocity of the fluid

v i :

Velocity of a bead

Wi :

Wiener index

cPPA:

Cyclic poly(o-phthalaldehyde)

CST:

Coil-to-stretch transition

FTF:

Fast-transient-flow

MC:

Merocyanine

PAA:

Poly(acrylic acid)

PAM:

Poly(acrylamide)

PB:

Polybutadiene

PDMS:

Poly(dimethylsiloxanes)

PE:

Polyethylene

PEA:

Poly(ethyl acrylate)

PEO:

Polyethylene oxide

PiBA:

Poly(iso-butyl acrylate)

PMA:

Poly(methyl acrylate)

PMMA:

Poly(methyl methacrylate)

PnBA:

Poly(n-butyl acrylate)

PS:

Polystyrene

PtBA:

Poly (tert-butyl acrylate)

QSSF:

Quasi-static-state-flow

SP:

Spiropyran

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Acknowledgement

Financial support was provided by National Natural Science Foundation of China (No. 21304076) and China Postdoctoral Science Foundation (No.2013 M541857, No.2014 T70612).

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Authors and Affiliations

  1. Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, 361005, P. R. China

    Huan Zhang, Yangju Lin, Yuanze Xu & Wengui Weng

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  1. Huan Zhang
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  2. Yangju Lin
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  3. Yuanze Xu
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Correspondence to Wengui Weng .

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  1. Department of Chemistry, University of Liverpool, Liverpool, United Kingdom

    Roman Boulatov

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Zhang, H., Lin, Y., Xu, Y., Weng, W. (2014). Mechanochemistry of Topological Complex Polymer Systems. In: Boulatov, R. (eds) Polymer Mechanochemistry. Topics in Current Chemistry, vol 369. Springer, Cham. https://doi.org/10.1007/128_2014_617

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