Scribd Logo
Upload

Welcome to Scribd!

  • Trip 1997 5 181

    Uploaded by

    astrid.paelinck
    7 views6 pages

    Original Title

    TRIP_1997_5_181

    Copyright

    © © All Rights Reserved

    Available Formats

    PDF or read online from Scribd

    Did you find this document useful?

    Is this content inappropriate?

    Report this Document

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
    Flag for inappropriate content
    7 views6 pages

    Trip 1997 5 181

    Uploaded by

    astrid.paelinck

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
    Flag for inappropriate content
    of 6
    REVIEWS Solutions of Associative Polymers Michael Rubinstein and Andrey V. Dobry?) The existence of ‘tunable’ interactions in solutions of associative polymers provides a convenient control ofthe physical properties of these polymers. For example, by changing temperature or concentration we can conirol the viscosity. This feature alone makes associative poly -mers extremely valuable for a rsumber of industrial appli: cations ranging from rheology modifiers for coating 10 flocculents for waste-water treatment, Despite the variety ‘of physical mechanisms behind the association phenom- ‘ena, many properties of these systems can be understood within a framework of a relatively simple unified model In the present article we use this unified approach to outline the static and dynamic properties unique to the solutions of associative polymers. Macromolecules with attractive groups forma very inter- esting and important class of polymeric systems, that is, associative polymersi-5. This class includes charged polymers (ionomers, polyelectrolytes and polyampho- Iytes), block copolymers in strongly selective solvents, and polymers with hydrogen bonding. The considerable interest in these systems is due to their numerous appli- cations, such as theology modifiers®, adhesives, ad- sorbents, coatings, biomedical implants, flocculents for ‘waste-water treatment, surfactants and stabilizers for heterogeneous polymerizations, and suspending agents for pharmaceutical delivery systems ‘The associations between attractive groups lead to the formation of physical bonds. The difference between the chemical covalent bonds and the physical bonds is that the latter are reversible. We would like to distinguish two types of physical bonds: weak physical bonds that can be broken and formed on experimental timescales: and strong physical bonds that are stable during the time ‘of the experiment but can be broken by changing experi- mental conditions (e.g. by heating). Examples of weak physical bonds include hydrogen bonds, multiplets in ionomers and micelles of block or raft copolymers in selective solvents. The bariers to break these weak physical bonds do not usually exceed 10-20 times the thermal energy kT (where & is the Boltzmann constant and T the absolute temperature). The lifetime of these bonds can vary from microseconds to seconds. Hence, polymers form and break these weak physical bonds many times during the course of the experiment. Examples of strong physical bonds are microcrystals, ouble and triple helices and other very strong associ- ations that could be effectively permanent under fixed ‘experimental conditions. Michael Rubinstein and Andrey V. Dobrynin Dept of Chemistry, Venable Hali CB#3290, The University of North Carolina, Chapel Hill, NC 27599-3290, USA (Fax: +1-919 962 2308. TRIP Vol 6,No 6. Juve 1997 Conyeant® 1997 Et leer Scie Ltd AN igh recnrund ORG A7@RARAIT AN 2th SANNA ATO ‘The structures formed in solutions of associating poly- mers depend on polymer concentration, the number of attractive groups per chain and the strength of physical bonds. In dilute solutions we may have self-association (formation of physical bonds between the attractive groups of the same chain) leading to partial collapse of the polymer as well as to aggregation of several mol- ecules into a complex (i.e. micelle). ‘At higher concentrations a transient network of poly ‘mer chains (physical gel) can be formed. This interchain aggregation into the physical network results in the increase of solution viscosity and the appearance of high elasticity. The classification of physical bonds into two types leads to an analogous classification for physical gels = strong and weak physical gels. The strong physical gels are soft solids and have finite elastic moduli on experi- mental timescales. In the network state their properties depend both on the preparation conditions under which the physical bonds were formed as well as on the test con- ditions. Strong physical gels are therefore analogous to (covalently bonded) chemical gels - their bonds are per- ‘manent at fixed experimental conditions. Weuk physical sgelsare qualitatively different from chemical gels and are loser to viscoelastic liquids. Most of the discussion below will be limited to the weak physical gels. ‘The presence of reversible crosslinks increases the effective attraction between polymers. reducing their affinity to the solvent. There: a delicate balance between aggregation and phase separation in these systems. Increasing the strength of attraction or the number of associating groups per chain leads to stronger aggregation and, in some cases, could result in separation into phases with different polymer concentrations. One classical example of associative polymers is the aqueous solutions of block copolymers, such as ethylene oxide-urethane copolymers‘, where hydrophobic and hydrophilic sequences alternate along the polymer chain, In this case the association is driven by the aggregation ‘of the hydrophobic blocks. At low concentrations these copolymers can form micelles that consist of compact hydrophobic cores surrounded by coronas of the soluble parts of the chains, At higher concentrations micelles aggregate into clusters of different morphologies!“

    You might also like