Tacticity (from Greek 'taktikos': of or relating to arrangement or order) is the relative
stereochemistryof adjacent chiral centers within a macromolecule[ "Introduction to polymers" R.J. Young ISBN 0412221705 ] . The practical significance of tacticity rests in the link between tacticity and the physical properties of the polymer. The regularity of the macromolecular structureinfluences the degree to which it has rigid, crystalline long range order or flexible, amorphouslong range disorder. Precise knowledge of tacticity of a polymer also helps understanding at what temperature a polymer melts, how solubleit is in a solventand its mechanical properties.
A tactic macromolecule in the
IUPACdefinition is a macromolecule in which essentially all the configurational (repeating) units are identical. Tacticity is particularly significant in vinyl polymers of the type -H2C-CH(R)- where each repeating unitwith a substituentR on one side of the polymer backboneis followed by the next repeating unit with the substituent on the same side as the previous one, the other side as the previous one or positioned randomly with respect to the previous one. In a hydrocarbon macromolecule with all carbon atoms making up the backbone in a tetrahedral molecular geometry, the zigzag backbone is in the paper plane with the substituents either sticking out of the paper or retreating into the paper. This projection is called the Natta projectionafter Giulio Natta. Monotactic macromolecules have one stereoisomeric atom per repeat unit, ditactic to n-tactic macromolecules have more than one stereoisomeric atom per unit.
Two adjacent structural units in a polymer molecule constitute a diad. If the diad consists of two identically oriented units, the diad is called a meso diad reflecting similar features as a
meso compound. If the diad consists of units oriented in opposition, the diad is called a racemo diad as in a racemiccompound. In the case of vinyl polymer molecules, a meso diad is one in which the substituent carbon chains are oriented on the same side of the polymer backbone.
The stereochemistry of macromolecules can be defined even more precisely with the introduction of triads. An isotactic triad (mm) is made up of two adjacent meso diads, a syndiotactic triad (rr) consists of two adjacent racemo diads and a heterotactic triad (rm) is composed of a meso diad adjacent to a racemo diad. The mass fraction of isotactic (mm) triads is a common quantitative measure of tacticity.
When the stereochemistry of a macromolecule is considered to be a
Bernoulli process, triad composition can be calculated from the probability of finding meso diads (Pm). When this probability is 0.25 then the probability of finding:
* an isotactic triad is Pm2 or 0.0625
* an heterotactic triad is 2Pm(1-Pm) or 0.375
* a syndiotactic triad is (1-Pm)2 or 0.5625with a total probability of 1. Similar relationships with diads exist for tetrads.
Tetrads, Pentads, etc.
The definition of tetrads and pentads introduce further sophistication and precision to defining tacticity, especially when information on long-range ordering is desirable. Tacticity measurements obtained by
Carbon-13NMR are typically expressed in terms of the relative abundance of various pentads within the polymer molecule, e.g. "mmmm", "mrrm".
Other conventions for quantifying tacticity
The primary convention for expressing tacticity is in terms of the relative weight fraction of triad or higher-order components, as described above. An alternative expression for tacticity is the average length of "meso" and "racemo" sequences within the polymer molecule. The average meso sequence length may be approximated from the relative abundance of pentads as follows: [Paukkeri, Ritva et al "Polymer" (1993), 34, 2488-2494.]
Isotactic polymers are composed of isotactic macromolecules (IUPAC definition). In
isotacticmacromolecules all the substituents are located on the same side of the macromolecular backbone. An isotactic macromolecule consists of 100% meso diads. Polypropyleneformed by Ziegler-Natta catalysis is an isotactic polymer.Fact|date=February 2007 Isotactic polymers are usually semicrystallineand often form a helix configuration.
syndiotacticor syntactic macromolecules the substituents have alternate positions along the chain. The macromolecule consists 100% of racemo diads. Syndiotactic polystyrene, made by metallocene catalysis polymerisation, is crystalline with a melting pointof 270 °C.Fact|date=February 2007
atacticmacromolecules the substituents are placed randomly along the chain. The percentage of meso diads is between 1 and 99%. With the aid of spectroscopic techniques such as NMR it is possible to pinpoint the composition of a polymer in terms of the percentages for each triad.Fact|date=February 2007
Polymers that are formed by free-radical mechanisms such as
polyvinylchlorideare usually atactic. Due to their random nature atactic polymers are usually amorphous. In hemiisotactic macromolecules every other repeat unit has a random substituent.
Atactic polymers are technologically very important. A good example is polystyrene (PS). If a special catalyst is used in its synthesis it is possible to obtain the syndiotactic version of this polymer, but most industrial polystyrene produced is atactic. The two materials have very different properties because the irregular structure of the atactic version makes it impossible for the polymer chains to stack in a regular fashion. The result is that whereas syndiotactic PS is a semicrystalline material, the more common atactic version cannot crystallize and forms a "glass" instead. This example is quite general in that many polymers of economic importance are atactic glass formers.
In vinyl polymers the complete configuration can be further described by defining polymer head/tail configuration. In a regular macromolecule all monomer units are normally linked in a head to tail configuration so that all β-substituents are separated by three carbon atoms. In head to head configuration this separation is only by 2 carbon atoms and the separation with tail to tail configuration is by 4 atoms. Head/tail configurations are not part of polymer tacticity but should be taken into account when considering polymer defects.
Techniques for measuring tacticity
Tacticity may be measured directly using
protonor carbon-13 NMR. This technique enables a quantitative assignment of degree of tacticity by integrating the peak area of a known diad (rr, mm, rm), triad (rrr, rrm, rmr, rmm, mrm, mmm) and/or higher order polymer subunits' frequency (ppm). Bernoullian or Markovian analysisof these peak areas then can be used to calculate the tacticity of the polymer [Wu, Ting Kai et al. "Macromolecules" 1977, "10", 529-531. ] .
Other techniques sensitive to tacticity include
x-ray powder diffraction, secondary ion mass spectroscopy (SIMS) [Vanden Eynde, X. et al. "Surf. Interf. Anal." 1997, "25", 41-45. ] , vibrational spectroscopy (FTIR) [Dybal, J. et al. "Macromolecules" 1990, "23", 1301-1308. ] and especially two-dimensional techniques. [ Schilling, Frederic et al "Macromolecules" 1985, "18", 1418-1422. ] . Tacticity may also be inferred by measuring another physical property, such as melting temperature, when the relationship between tacticity and that property is well-established.
* Tacticity @ Ecole Polytechnique Fédérale de Lausanne [http://web.archive.org/web/20040612172217/http://scgc.epfl.ch/load/cours_chim/cwandrey_part-2-1.pdf] [http://scgc.epfl.ch/load/cours_chim/cwandrey_part-2-1.pdf]
IUPACmacromolecular glossary [http://www.iupac.org/reports/1996/6812jenkins/molecules.html]
* Application of spectroscopy in polymer charactisation & UCLA Los Angeles [http://www.chemeng.ucla.edu/che112/Notes/polymer%20spectroscopy.pdf]
* Polymer Structure [http://openlearn.open.ac.uk/mod/resource/view.php?id=196631]
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