Chemistry:Polymerization-induced phase separation

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Polymerization-induced phase separation (PIPS) is the occurrence of phase separation in a multicomponent mixture induced by the polymerization of one or more components.[1][2] The increase in molecular weight of the reactive component renders one or more components to be mutually immiscible in one another, resulting in spontaneous phase segregation.

Types

Polymerization-induced phase separation can be initiated either through thermally induced polymerization or photopolymerization.[3][4][5] The process general occurs through spinodal decomposition, commonly resulting in the formation of co-continuous phases.[6]

Control over morphology

The morphology of the final phase separated structures are generally random owing to the stochastic nature of the onset and process of phase separation. Several approaches have been investigated to control morphology. Tran-Cong-Miyata and co-workers using periodic irradiation in photoreactive polymer blends to control morphology, specifically width of the resultant spinodal modes in the phase separated morphology.[7] Li and co-workers employed holography, a process of holographic polymerization, in to order to direct the phase separated structure to have the same patterns as the holographic field.[8] Recently, Hosein and co-workers demonstrated that nonlinear optical pattern formations that occur in photopolymer systems may be used to direct the organization of blends to have the same morphology as the light pattern.[9]

Applications

The process is commonly used in control of the morphology of polymer blends, for applications in thermoelectrics, solid-state lighting, polymer electrolytes, composites, membrane formation, and surface pattern formations.[10]

References

  1. Kim, J. Y. (1993-01-01). "Polymerization-induced phase separation in a liquid-crystal-polymer mixture". Physical Review Letters 71 (14): 2232–2235. doi:10.1103/PhysRevLett.71.2232. PMID 10054621. Bibcode1993PhRvL..71.2232K. http://ideaexchange.uakron.edu/cgi/viewcontent.cgi?article=1067&context=polymer_ideas. 
  2. Nephew, J. B. (1998-01-01). "Reaction-Induced Phase Separation Dynamics: A Polymer in a Liquid Crystal Solvent". Physical Review Letters 80 (15): 3276–3279. doi:10.1103/PhysRevLett.80.3276. Bibcode1998PhRvL..80.3276N. 
  3. Amundson, Karl (1997-01-01). "Morphology and electro-optic properties of polymer-dispersed liquid-crystal films". Physical Review E 55 (2): 1646–1654. doi:10.1103/PhysRevE.55.1646. Bibcode1997PhRvE..55.1646A. 
  4. Nwabunma, Domasius; Chiu, Hao-Wen; Kyu, Thein (2000-10-02). "Theoretical investigation on dynamics of photopolymerization-induced phase separation and morphology development in nematic liquid crystal/polymer mixtures". The Journal of Chemical Physics 113 (15): 6429–6436. doi:10.1063/1.1309537. ISSN 0021-9606. Bibcode2000JChPh.113.6429N. 
  5. Tran-Cong-Miyata, Qui; Nakanishi, Hideyuki (2017-02-01). "Phase separation of polymer mixtures driven by photochemical reactions: current status and perspectives" (in en). Polymer International 66 (2): 213–222. doi:10.1002/pi.5243. ISSN 1097-0126. 
  6. Tran-Cong-Miyata, Qui; Nakanishi, Hideyuki (2017-02-01). "Phase separation of polymer mixtures driven by photochemical reactions: current status and perspectives" (in en). Polymer International 66 (2): 213–222. doi:10.1002/pi.5243. ISSN 1097-0126. 
  7. Tran-Cong-Miyata, Qui; Nishigami, Shinsuke; Ito, Tetsuo; Komatsu, Satonori; Norisuye, Tomohisa (2004-07-01). "Controlling the morphology of polymer blends using periodic irradiation" (in en). Nature Materials 3 (7): 448–451. doi:10.1038/nmat1150. ISSN 1476-1122. PMID 15184893. Bibcode2004NatMa...3..448T. 
  8. Smith, Derrick M.; Li, Christopher Y.; Bunning, Timothy J. (2014-02-01). "Light-directed mesoscale phase separation via holographic polymerization" (in en). Journal of Polymer Science Part B: Polymer Physics 52 (3): 232–250. doi:10.1002/polb.23413. ISSN 1099-0488. Bibcode2014JPoSB..52..232S. 
  9. Biria, Saeid; Malley, Phillip P. A.; Kahan, Tara F.; Hosein, Ian D. (2016-11-15). "Optical Autocatalysis Establishes Novel Spatial Dynamics in Phase Separation of Polymer Blends during Photocuring". ACS Macro Letters 5 (11): 1237–1241. doi:10.1021/acsmacrolett.6b00659. 
  10. Karim, A.; Slawecki, T. M.; Kumar, S. K.; Douglas, J. F.; Satija, S. K.; Han, C. C.; Russell, T. P.; Liu, Y. et al. (1998-02-01). "Phase-Separation-Induced Surface Patterns in Thin Polymer Blend Films". Macromolecules 31 (3): 857–862. doi:10.1021/ma970687g. ISSN 0024-9297. Bibcode1998MaMol..31..857K.