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Phase state and rheology of polyisobutylene blends with silicone resin

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Abstract

Silicone resins are hyperbranched macromolecules, which are nearly spherical in shape, nanometer in size, and covered with numerous terminal organic groups. For this reason, they can play a role of functionalized silica nanoparticles that are miscible with a polymer medium. In this paper, mixtures of linear polyisobutylene (PIB) with methyl-terminated silicone MT resin are considered. The phase states of mixtures were studied by laser interferometry method accompanied with rheological tests. It turned out that the solubility of the silicone resin in PIB matrix does not exceed a few percent even at high temperatures. Nevertheless, the addition of the resin significantly reduces the effective viscosity of PIB due to the shear-induced interlayer slip. To describe the concentration dependence of the blend viscosity, various empirical equations were considered, and their combination to describe the viscosity of blends in different phase states by one equation was proposed.

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References

  • Amirova AI, Golub OV, Meshkov IB, Migulin DA, Muzafarov AM, Filippov AP (2015) Solution behavior of hyperbranched polymethylsilsesquioxane with intramolecular cycles. Int J Polym Anal Charact 20(3):268–276

    Article  CAS  Google Scholar 

  • Anokhina TS, Ilyin SO, Ignatenko VY, Bakhtin DS, Kostyuk AV, Antonov SV, Volkov AV (2019) Formation of porous films with hydrophobic surface from a blend of polymers. Polym Sci Ser A 61(5):619–626

    Article  CAS  Google Scholar 

  • Antonow GN (1907) Sur la tension superficielle a la limite de deux couches. J Chim Phys 5:372–385

    Article  CAS  Google Scholar 

  • Arrhenius S (1887) Über die innere Reibung verdünnter wässeriger Lösungen. Z Physik Chem 1:285–298

    Google Scholar 

  • Baumann TF, Jones TV, Wilson T, Saab AP, Maxwell RS (2009) Synthesis and characterization of novel PDMS nanocomposites using POSS derivatives as cross-linking filler. J Polym Sci Part A 47(10):2589–2596

    Article  CAS  Google Scholar 

  • Carr PL, Davies GR, Feast WJ, Stainton NM, Ward IM (1996) Dielectric and mechanical characterization of aryl ester dendrimer/PET blends. Polymer 37(12):2395–2401

    Article  CAS  Google Scholar 

  • Chacko RT, Ventura J, Zhuang J, Thayumanavan S (2012) Polymer nanogels: a versatile nanoscopic drug delivery platform. Adv Drug Deliv Rev 64(9):836–851

    Article  CAS  Google Scholar 

  • Chalykh AE, Gerasimov VK (2004) Phase equilibria and phase structures of polymer blends. Russ Chem Rev 73(1):59–74

    Article  CAS  Google Scholar 

  • Chen D, Chen F, Hu X, Zhang H, Yin X, Zhou Y (2015) Thermal stability, mechanical and optical properties of novel addition cured PDMS composites with nano-silica sol and MQ silicone resin. Compos Sci Technol 117:307–314

    Article  CAS  Google Scholar 

  • Chen W, Lupton KE, Romenesko DJ, Schmidt RG, Zhang H (1999) Organic polymers modified with thermoplastic silicone blends. US Patent:5861450

  • Chuang HK, Han CD (1984) Rheological behavior of polymer blends. J Appl Polym Sci 29:2205–2229

    Article  CAS  Google Scholar 

  • Clarson SJ, Semlyen JA (1993) Siloxane polymers. Prentice Hall, New Jersey

    Google Scholar 

  • Cox WP, Merz EH (1958) Correlation of dynamic and steady flow viscosities. J Polym Sci 28(118):619–622

    Article  CAS  Google Scholar 

  • Deng F, Wang X, He D, Hu J, Gong C, Ye YS, Xie X, Xue Z (2015) Microporous polymer electrolyte based on PVDF/PEO star polymer blends for lithium ion batteries. J Membr Sci 491:82–89

    Article  CAS  Google Scholar 

  • Derkach SR (2009) Rheology of emulsions. Adv Colloid Interf Sci 151(1–2):1–23

    Article  CAS  Google Scholar 

  • Edmondson S, Osborne VL, Huck WTS (2004) Polymer brushes via surface-initiated polymerizations. Chem Soc Rev 33:14–22

    Article  CAS  Google Scholar 

  • Flagg DH, McCarthy TJ (2016) Rediscovering silicones: MQ copolymers. Macromolecules 49(22):8581–8592

    Article  CAS  Google Scholar 

  • Grace HP (1982) Dispersion phenomena in high viscosity immiscible fluid systems and application of static mixers as dispersion devices in such systems. Chem Eng Commun 14(3–6):225–277

    Article  CAS  Google Scholar 

  • Guido S, Simeone M, Villone M (1999) Diffusion effects on the interfacial tension of immiscible polymer blends. Rheol Acta 38:287–296

    Article  CAS  Google Scholar 

  • Han CD, Kim J, Kim JK (1989) Determination of the order-disorder transition temperature of block copolymers. Macromolecules 22(1):383–394

    Article  CAS  Google Scholar 

  • Hashimoto T, Takebe T, Asakawa K (1993) Phase transition of polymer mixtures under simple shear flow. Physica Part A 194(1–4):338–351

    Article  CAS  Google Scholar 

  • Hayashi H, Flory PJ, Wignall GD (1983) Configuration of the polyisobutylene chain according to neutron and X-ray scattering. Macromolecules 16(8):1328–1335

    Article  CAS  Google Scholar 

  • Heitmiller RF, Naar RZ, Zabusky HH (1964) Effect of homogeneity on viscosity in capillary extrusion of polyethylene. J Appl Polym Sci 8(2):873–880

    Article  CAS  Google Scholar 

  • Hennequin Y, Evens M, Angulo CMQ, van Duijneveldt JS (2005) Miscibility of small colloidal spheres with large polymers in good solvent. J Chem Phys 123(054906):1–8

    Google Scholar 

  • Holtel D, Burgath A, Frey H (1997) Degree of branching in hyperbranched polymers. Acta Polymer 48:30–35

    Article  Google Scholar 

  • Huang J, Turner SR (2018) Hypercrosslinked polymers: a review. Polym Rev 58:1–41

    Article  CAS  Google Scholar 

  • Hurd CB (1946) Studies on siloxanes. I. The specific volume and viscosity in relation to temperature and constitution. J Am Chem Soc 68:364–370

    Article  CAS  Google Scholar 

  • Ignatenko VY, Anokhina TS, Ilyin SO, Kostyuk AV, Bakhtin DS, Antonov SV, Volkov AV (2020) Fabrication of microfiltration membranes from polyisobutylene/polymethylpentene blends. Polym Int 69(2):165–172

    Article  CAS  Google Scholar 

  • Ilyin SO, Kulichikhin VG, Malkin AY (2016a) The rheological characterisation of typical injection implants based on hyaluronic acid for contour correction. Rheol Acta 55(3):223–233

    Article  CAS  Google Scholar 

  • Ilyin SO, Makarova VV, Anokhina TS, Ignatenko VY, Brantseva TV, Volkov AV, Antonov SV (2018) Diffusion and phase separation at the morphology formation of cellulose membranes by regeneration from N-methylmorpholine N-oxide solutions. Cellulose 25(4):2515–2530

    Article  CAS  Google Scholar 

  • Ilyin SO, Polyakova MY, Makarova VV, Meshkov IB, Kulichikhin VG (2016b) Phase state and rheology of organosilicon nanocomposites with functionalized hyperbranched nanoparticles. Polym Sci Ser A 58(6):985–993

    Article  CAS  Google Scholar 

  • Iza M, Bousmina M (2000) Nonlinear rheology of immiscible polymer blends: step strain experiments. J Rheol 44:1363–1384

    Article  CAS  Google Scholar 

  • Jackson NE, Tucker CL III (2003) A model for large deformation of an ellipsoidal droplet with interfacial tension. J Rheol 47:659–682

    Article  CAS  Google Scholar 

  • Jia P, Liu H, Liu Q, Cai X (2016) Thermal degradation mechanism and flame retardancy of MQ silicone/epoxy resin composites. Polym Degrad Stab 134:144–150

    Article  CAS  Google Scholar 

  • Kakkar A (2017) Miktoarm star polymers: from basics of branched architecture to synthesis, self-assembly and applications. Royal Society of Chemistry, London

    Book  Google Scholar 

  • Kammer HW, Kummerloewe C, Kressler J, Melior JP (1991) Shear-induced phase changes in polymer blends. Polymer 32(8):1488–1492

    Article  CAS  Google Scholar 

  • Kango S, Kalia S, Celli A, Njuguna J, Habibi Y, Kumar R (2013) Surface modification of inorganic nanoparticles for development of organic–inorganic nanocomposites—a review. Prog Polym Sci 38(8):1232–1261

    Article  CAS  Google Scholar 

  • Karpukhina EA, Ilyin SO, Makarova VV, Meshkov IB, Kulichikhin VG (2014) Phase state and rheology of polyisobutylene mixtures with decyl surface modified silica nanoparticles. Polym Sci Ser A 56(6):798–811

    Article  CAS  Google Scholar 

  • Kazakova VV, Rebrov EA, Myakushev VB, Strelkova TV, Ozerin AN, Ozerina LA, Chenskaya TB, Sheiko SS, Sharipov EY, Muzafarov AM (2000) From a hyperbranched polyethoxysiloxane toward molecular forms of silica: a polymer-based approach to the monitoring of silica properties. ACS Symp Ser 729:503–515

    Article  CAS  Google Scholar 

  • Kopesky ET, Haddad TS, McKinley GH, Cohen RE (2005) Miscibility and viscoelastic properties of acrylic polyhedral oligomeric silsesquioxane–poly (methyl methacrylate) blends. Polymer 46(13):4743–4752

    Article  CAS  Google Scholar 

  • Kumar SK, Jouault N, Benicewicz B, Neely T (2013) Nanocomposites with polymer grafted nanoparticles. Macromolecules 46(9):3199–3214

    Article  CAS  Google Scholar 

  • Lederer A, Burchard W (2015) Hyperbranched polymers: macromolecules in between deterministic linear chains and dendrimer structures. Royal Society of Chemistry, London

    Google Scholar 

  • Lee JH, Archer LA (2002) Stress relaxation of star/linear polymer blends. Macromolecules 35(17):6687–6696

    Article  CAS  Google Scholar 

  • Li S, Lin Q, Cui C (2016) The effect of core–shell particles on the mechanical performance of epoxy resins modified with hyperbranched polymers. J Mater Res 31(10):1393–1402

    Article  CAS  Google Scholar 

  • Liao YT, Lin YC, Kuo SW (2017) Highly thermally stable, transparent, and flexible polybenzoxazine nanocomposites by combination of double-decker-shaped polyhedral silsesquioxanes and polydimethylsiloxane. Macromolecules 50(15):5739–5747

    Article  CAS  Google Scholar 

  • Lin CC (1979) A mathematical model for viscosity in capillary extrusion of two-component polyblends. Polym J 11(3):185–192

    Article  CAS  Google Scholar 

  • Liu Q, Bao X, Deng S, Cai X (2014) The investigation of methyl phenyl silicone resin/epoxy resin using epoxy-polysiloxane as compatibilizer. J Therm Anal Calorim 118(1):247–254

    Article  CAS  Google Scholar 

  • Lucas P, Robin JJ (2007) Silicone-based polymer blends: an overview of the materials and processes. Adv Polym Sci 209:111–147

    CAS  Google Scholar 

  • Lucassen-Reynders EH (1993) Interfacial viscoelasticity in emulsions and foams. Food Struct 12(1):1–12

    CAS  Google Scholar 

  • Ma PC, Siddiqui NA, Marom G, Kim JK (2010) Dispersion and functionalization of carbon nanotubes for polymer-based nanocomposites: a review. Compos Part A 41(10):1345–1367

    Article  CAS  Google Scholar 

  • Maffettone PL, Greco F (2004) Ellipsoidal drop model for single drop dynamics with non-Newtonian fluids. J Rheol 48(1):83–100

    Article  CAS  Google Scholar 

  • Maffettone PL, Minale M (1998) Equation of change for ellipsoidal drops in viscous flow. J Non-Newtonian Fluid Mech 78(2–3):227–241

    Article  CAS  Google Scholar 

  • Malkin AY, Semakov AV, Kulichikhin VG (2010) Self-organization in the flow of complex fluids (colloid and polymer systems): Part 1: experimental evidence. Adv Colloid Interf Sci 157(1–2):75–90

    Article  CAS  Google Scholar 

  • Makarova V, Kulichikhin V (2012) Application of interferometry to analysis of polymer-polymer and polymer-solvent interactions. In: Padron I (ed) Interferometry. Research and Applications in Science and Technology. InTech, Rijeka, pp 395–436

    Google Scholar 

  • Marom G, Wagner HD (2017) Should polymer nanocomposites be regarded as molecular composites? J Mater Sci 52:8357–8361

    Article  CAS  Google Scholar 

  • Marteaux L, Liles DT (2016) Silicone Dispersions. CRC Press, Boca Raton

  • McLeish TCB, O'Connor KP (1993) Rheology of star-linear polymer blends: molecular tube models. Polymer 34(14):2998–3003

    Article  CAS  Google Scholar 

  • Marzi D, Capone B, Marakis J, Merola MC, Truzzolillo D, Cipelletti L, Moingeon F, Gauthier M, Vlassopoulos D, Likos CN, Camargo M (2015) Depletion, melting and reentrant solidification in mixtures of soft and hard colloids. Soft Matter 11(42):8296–8312

    Article  CAS  Google Scholar 

  • Metelkin VI, Blekht VS (1984) Formation of a continuous phase in heterogeneous polymer mixtures. Colloid J 46(3):425–429

    Google Scholar 

  • Mezzenga R, Boogh L, Månson JAE (2001) A review of dendritic hyperbranched polymer as modifiers in epoxy composites. Compos Sci Technol 61(5):787–795

    Article  CAS  Google Scholar 

  • Migulin D, Tatarinova E, Meshkov I, Cherkaev G, Vasilenko N, Buzin M, Muzafarov A (2016) Synthesis of the first hyperbranched polyorganoethoxysilsesquioxanes and their chemical transformations to functional core–shell nanogel systems. Polym Int 65:72–83

    Article  CAS  Google Scholar 

  • Minale M (2004) Deformation of a non-Newtonian ellipsoidal drop in a non-Newtonian matrix: extension of Maffettone–Minale model. J Non-Newton Fluid Mech 123(2–3):151–160

    Article  CAS  Google Scholar 

  • Minale M (2010) Models for the deformation of a single ellipsoidal drop: a review. Rheol Acta 49(8):789–806

    Article  CAS  Google Scholar 

  • Minale M, Moldenaers P, Mewis J (1997) Effect of shear history on the morphology of immiscible polymer blends. Macromolecules 30(18):5470–5475

    Article  CAS  Google Scholar 

  • Nunez CM, Andrady AL, Guo RK, Baskir JN, Morgan DR (1998) Mechanical properties of blends of PAMAM dendrimers with poly(vinyl chloride) and poly(vinyl acetate). J Polym Sci Part A 36:2111–2117

    Article  CAS  Google Scholar 

  • Nunez CM, Chiou BS, Andrady AL, Khan SA (2000) Solution rheology of hyperbranched polyesters and their blends with linear polymers. Macromolecules 33(5):1720–1726

    Article  CAS  Google Scholar 

  • Ohno K, Morinaga T, Takeno S, Tsujii Y, Fukuda T (2007) Suspensions of silica particles grafted with concentrated polymer brush: effects of graft chain length on brush layer thickness and colloidal crystallization. Macromolecules 40(25):9143–9150

    Article  CAS  Google Scholar 

  • Olabisi O, Robeson LM, Shaw MT (1979) Polymer-polymer miscibility. Academic Press, New York

    Google Scholar 

  • Paul DR, Barlow JW (1980) Polymer blends. J Macromol Sci Rev Macromol Chem 18(1):109–168

    Article  Google Scholar 

  • Peng X, Huang Y, Xia T, Kong M, Li G (2011) Shapes of dispersed phase in confined PIB/PDMS blends with different compositions during shear flow. Eur Polym J 47(10):1956–1963

    CAS  Google Scholar 

  • Rahman IA, Padavettan V (2012) Synthesis of silica nanoparticles by sol-gel: size-dependent properties, surface modification, and applications in silica-polymer nanocomposites—a review. J Nanomater 2012:1687–4110

    Article  CAS  Google Scholar 

  • Ratna D, Varley R, Raman RS, Simon GP (2003) Studies on blends of epoxy-functionalized hyperbranched polymer and epoxy resin. J Mater Sci 38(1):147–154

    Article  CAS  Google Scholar 

  • Ristić S, Mijović J (2008) Dynamics in complex systems: Dendrimer–polymer blends in electric and mechanical fields. Polymer 49(21):4695–4702

    Article  CAS  Google Scholar 

  • Robins MM (2000) Emulsions—creaming phenomena. Curr Opin Colloid Interface Sci 5:265–272

    Article  CAS  Google Scholar 

  • Roldugin VI, Serenko OA, Getmanova EV, Novozhilova NA, Nikifirova GG, Buzin MI, Chvalun SN, Ozerin AN, Muzafarov AM (2016) Effect of hybrid nanoparticles on glass transition temperature of polymer nanocomposites. Polym Compos 37(7):1978–1990

    Article  CAS  Google Scholar 

  • Rothon R (2017) Fillers for polymer applications. Springer, Cham

    Book  Google Scholar 

  • van Ruymbeke E, Coppola S, Balacca L, Righi S, Vlassopoulos D (2010) Decoding the viscoelastic response of polydisperse star/linear polymer blends. J Rheol 54(3):507–538

    Article  CAS  Google Scholar 

  • Schmaljohann D, Pötschke P, Hässler R, Voit BI, Froehling PE, Mostert B, Loontjens JA (1999) Blends of amphiphilic, hyperbranched polyesters and different polyolefins. Macromolecules 32(19):6333–6339

    Article  CAS  Google Scholar 

  • Serenko OA, Roldugin VI, Novozhilova NA, Soldatov MA, Nikiforova GG, Mironova MV, Ilyin SO, Kulichikhin VG, Muzafarov AM (2015) Phase structure and properties of blends based on polystyrene and carbosilane dendrimers. Polym Sci Ser A 57(5):586–595

    Article  CAS  Google Scholar 

  • Shi X, Chen Z, Yang Y (2014) Toughening of poly (l-lactide) with methyl MQ silicone resin. Eur Polym J 50:243–248

    Article  CAS  Google Scholar 

  • Sperling RA, Parak WJ (2010) Surface modification, functionalization and bioconjugation of colloidal inorganic nanoparticles. Phil Trans R Soc Part A 368:1333–1383

    Article  CAS  Google Scholar 

  • Thomas S, Grohens Y, Jyotishkumar P (2015) Characterization of polymer blends. Wiley, Weinheim

    Google Scholar 

  • Thomas S, Muller R, Abraham J (2016) Rheology and processing of polymer nanocomposites. Wiley, Hoboken

    Book  Google Scholar 

  • Utracki LA (1991) On the viscosity-concentration dependence of immiscible polymer blends. J Rheol 35(8):1615–1637

    Article  CAS  Google Scholar 

  • Utracki LA, Wilkie CA (2014) Polymer blends handbook, 2nd edn. Springer, Dordrecht

    Google Scholar 

  • Vögtle F, Richardt G, Werner N (2009) Dendrimer chemistry. Wiley, Weinheim

    Book  Google Scholar 

  • Vshivkov SA, Kulichikhin SG, Rusinova EV (1998) Phase transitions in polymer solutions induced by mechanical fields. Russ Chem Rev 67(3):233–243

    Article  Google Scholar 

  • Xanthos M (2010) Functional fillers for plastics, 2nd edn. Wiley, Weinheim

    Book  Google Scholar 

  • Yu W, Bousmina M (2003) Ellipsoidal model for droplet deformation in emulsions. J Rheol 47:1011–1039

    Article  CAS  Google Scholar 

  • Zhang JF, Sun X (2004) Mechanical properties and crystallization behavior of poly (lactic acid) blended with dendritic hyperbranched polymer. Polym Int 53(6):716–722

    Article  CAS  Google Scholar 

  • Zhang W, Camino G, Yang R (2017) Polymer/polyhedral oligomeric silsesquioxane (POSS) nanocomposites: an overview of fire retardance. Prog Polym Sci 67:77–125

    Article  CAS  Google Scholar 

  • Zhang Y, Yang X, Zhao X, Huang W (2012) Synthesis and properties of optically clear silicone resin/epoxy resin hybrids. Polym Int 61:294–300

    Article  CAS  Google Scholar 

  • Zhao J, Fu Y, Liu S (2008) Polyhedral oligomeric silsesquioxane (POSS)-modified thermoplastic and thermosetting nanocomposites: a review. Polym Polym Compos 16(8):483–500

    CAS  Google Scholar 

  • Zhiltsov A, Gritsenko O, Kazakova V, Gorbatsevitch O, Bessonova N, Askadskii A, Serenko O, Muzafarov A (2015) Polylactide and hybrid silicasol nanoparticle-based composites. J Appl Polym Sci 132(17):41894–41903

    Article  CAS  Google Scholar 

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Acknowledgments

The authors express gratitude to Dr. Prof. A.M. Muzafarov for providing the silicone resins.

Funding

This research was supported by the Russian Science Foundation (project 17-79-30108, the silicone resins for this research and rheological characterization) and the Council for Grants of the President of the Russian Federation (project No. MK-545.2017.3, the study of silicon resin blends with linear polyisobutylene).

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  1. A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninsky Prospect, 119991, Moscow, Russia

    Sergey O. Ilyin, Veronika V. Makarova, Mariya Y. Polyakova & Valery G. Kulichikhin

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  1. Sergey O. Ilyin
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  2. Veronika V. Makarova
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  3. Mariya Y. Polyakova
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Correspondence to Sergey O. Ilyin.

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Ilyin, S.O., Makarova, V.V., Polyakova, M.Y. et al. Phase state and rheology of polyisobutylene blends with silicone resin. Rheol Acta 59, 375–386 (2020). https://doi.org/10.1007/s00397-020-01208-6

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