Sorbitol-type nucleating agents can be used to aid dispersion of polyhedral oligomeric silsesquioxane (POSS) molecules in isotactic polypropylene (iPP) and to promote self-assembly of POSS molecules into nanoparticles. In this paper, the interactions between a sorbitol-type nucleating agent and POSS molecules were investigated using polarized optical microscopy and rotational rheometry. Dibenzylidene sorbitol (DBS), a nucleating agent of iPP, was used in conjunction with two non-reactive POSS—trisilanolphenyl-POSS (ph-TPOSS) and octaisobutyl-POSS (bu-MPOSS). DBS formed three-dimensional fibrillar networks in iPP upon cooling from a homogeneous state. These fibrillar networks were characterized as gels using oscillatory shear rheometry. Trisilanolphenyl-POSS was incompatible with iPP but offered strong hydrogen bonding possibility with DBS; bu-MPOSS, on the other hand, was compatible with iPP but did not produce significant interactions with DBS. It was found that as low as 0.5 wt % of ph-TPOSS molecules in a ternary compound with 0.7 wt % DBS subdued fibrillar network formation by DBS and altered the rheological properties of the compounds. No such effect was seen in compounds of bu-MPOSS, although viscosity showed strong reduction. The storage modulus vs loss modulus data provided much better indication of changes of morphology in iPP/POSS and iPP/DBS/POSS compounds than loss tangent vs oscillatory frequency plots.
REFERENCES
1.
Arai
, M.
, M.
Kanamaru
, T.
Matsumura
, Y.
Hattori
, S.
Utsumi
, T.
Ohba
, H.
Tanaka
, C. M.
Yang
, H.
Kanoh
, F.
Okino
, H.
Touhara
, and K.
Kaneko
, “Pore characterization of assembly-structure controlled single wall carbon nanotube
,” Adsorption
13
, 509
–514
(2007
).2.
Balzano
, L.
, G.
Portale
, G. W. M.
Peters
, and S.
Rastogi
, “Thermoreversible DMDBS phase separation in iPP: The effects of flow on the morphology
,” Macromolecules
41
, 5350
–5355
(2008b
).3.
Balzano
, L.
, S.
Rastogi
, and G. W. M.
Peters
, “Flow induced crystallization in isotactic polypropylene–1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol blends: Implications on morphology of shear and phase separation
,” Macromolecules
41
, 399
–408
(2008a
).4.
Barry
, A. J.
, W. H.
Daudt
, J. J.
Domicone
, and J. W.
Gilkey
, “Crystalline organosilsesquioxanes
,” J. Am. Chem. Soc.
77
, 4248
–4252
(1955
).5.
Brown
, J. F.
, and L. H.
Vogt
, “The polycondensation of cyclohexylsilanetriol
,” J. Am. Chem. Soc.
87
, 4313
–4317
(1965
).6.
Choi
, S.
, N. Y.
Vaidya
, C. D.
Han
, N.
Sota
, and T.
Hashimoto
, “Effects of sample preparation method and thermal history on phase transition in highly asymmetric block copolymer: Comparison with symmetric block copolymers
,” Macromolecules
36
, 7707
–7720
(2003
).7.
Dolgopolsky
, I.
, A.
Silberman
, and S.
Kenig
, “The effect of nucleating agents on the crystallization kinetics of polypropylene
,” Polym. Adv. Technol.
6
, 653
–661
(1995
).8.
Esteves
, I. A. A. C.
, F. J. A. L.
Cruz
, E. A.
Müller
, S.
Agnihotri
, and J. P. B.
Mota
, “Determination of the surface area and porosity of carbon nanotube bundles from a Langmuirian analysis of sub- and supercritical adsorption data
,” Carbon
47
, 948
–956
(2009
).9.
Fahrländer
, M.
, K.
Fuchs
, and C.
Friedrich
, “Rheological properties of dibenzylidene sorbitol networks in poly(propylene oxide) matrices
,” J. Rheol.
44
, 1103
–1119
(2000
).10.
Fasce
, D. P.
, R. J. J.
Williams
, F.
Méchin
, J. P.
Pascault
, M. F.
Llauro
, and R.
Pétiaud
, “Synthesis and characterization of polyhedral silsesquioxanes bearing bulky functionalized substituents
,” Macromolecules
32
, 4757
–4763
(1999
).11.
Feher
, F. J.
, T. A.
Budzichowski
, R. L.
Blanski
, K. J.
Weller
, and J. W.
Ziller
, “Facile syntheses of new incompletely condensed polyhedral oligosilsesquioxanes: [(c-C5H9)7Si7O9(OH)3], [(c-C7H13)7Si7O9(OH)3], and [(c-C7H13)6Si6O7(OH)4]
,” Organometallics
10
, 2526
–2528
(1991
).12.
Feher
, F. J.
, and D. A.
Newman
, “Enhanced silylation reactivity of a model for silica surfaces
,” J. Am. Chem. Soc.
112
, 1931
–1936
(1990
).13.
Feher
, F. J.
, D. A.
Newman
, and J. F.
Walzer
, “Silsesquioxanes as models for silica surfaces
,” J. Am. Chem. Soc.
111
, 1741
–1748
(1989
).14.
Feher
, F. J.
, S. H.
Phillips
, and J. W.
Ziller
, “Facile and remarkably selective substitution reactions involving framework silicon atoms in silsesquioxane frameworks
,” J. Am. Chem. Soc.
119
, 3397
–3398
(1997
).15.
Feng
, Y.
, X.
Jin
, and N.
Hay
, “Effect of nucleating agent addition on crystallization of isotactic polypropylene
,” J. Appl. Polym. Sci.
69
, 2089
–2095
(1998
).16.
Fina
, A.
, D.
Tabuani
, A.
Frache
, and G.
Camino
, “Polypropylene-polyhedral oligomeric silsesquioxanes (POSS) nanocomposites
,” Polymer
46
, 7855
–7866
(2005
).17.
Fu
, B. X.
, M. Y.
Gelfer
, B. S.
Hsiao
, S.
Phillips
, B.
Viers
, R.
Blanski
, and P.
Ruth
, “Physical gelation in ethylene–propylene copolymer melts induced by polyhedral oligomeric silsesquioxane (POSS) molecules
,” Polymer
44
, 1499
–1506
(2003
).18.
Fu
, B. X.
, L.
Yang
, R. H.
Somani
, S. X.
Zong
, B. S.
Hsiao
, S.
Phillips
, R.
Blanski
, and P.
Ruth
, “Crystallization studies of isotactic polypropylene containing nanostructured polyhedral oligomeric silsesquioxane molecules under quiescent and shear conditions
,” J. Polym. Sci., Part B: Polym. Phys.
39
, 2727
–2739
(2001
).19.
Fujiyama
, M.
, and T.
Wakino
, “Structures and properties of injection moldings of crystallization nucleator-added polypropylenes. I. Structure-property relationships
,” J. Appl. Polym. Sci.
42
, 2739
–2747
(1991
).20.
Guenet
, J. -M.
, “Microfibrillar networks: Polymer thermoreversible gels vs organogels
,” Macromol. Symp.
241
, 45
–50
(2006
).21.
Han
, C. D.
, and J.
Kim
, “Rheological technique for determining the order-disorder transition of block copolymers
,” J. Polym. Sci., Polym. Phys. Ed.
24
, 1741
–1764
(1987
).22.
Han
, C. D.
, J.
Kim
, and J. K.
Kim
, “Determination of the order-disorder transition of block copolymers
,” Macromolecules
22
, 383
–394
(1989
).23.
Han
, C. D.
, N. Y.
Vaidya
, D.
Kim
, G.
Shin
, D.
Yamaguchi
, and T.
Hashimoto
, “Lattice disordering/ordering and demicellization/micellization transitions in highly asymmetric polystyrene-block-polyisoprene copolymers
,” Macromolecules
33
, 3767
–3780
(2000
).24.
Huang
, J.
, C.
He
, Y.
Xiao
, K. Y.
Mya
, J.
Dai
, and Y. P.
Siow
, “Polyimide/POSS nanocomposites: Interfacial interaction, thermal properties and mechanical properties
,” Polymer
44
, 4491
–4499
(2003
).25.
Jeon
, H. G.
, P. T.
Mather
, and T. S.
Haddad
, “Shape memory and nanostructure in poly(norbornyl-POSS) copolymers
,” Polym. Int.
49
, 453
–457
(2000
).26.
Kim
, Y. C.
, C. Y.
Kim
, and S. C.
Kim
, “Crystallization characteristics of isotactic polypropylene with and without nucleating agents
,” Polym. Eng. Sci.
31
, 1009
–1014
(1991
).27.
Kojima
, Y.
, A.
Usuki
, M.
Kawasumi
, A.
Okada
, T.
Kurauchi
, and O.
Kamigaito
, “Synthesis of nylon 6-clay hybrid by montmorillonite intercalated with-caprolactam
,” J. Polym. Sci., Part A: Polym. Chem.
31
, 983
–986
(1993
).28.
Kristiansen
, M.
, T.
Tervoort
, P.
Smith
, and H.
Goossens
, “Mechanical properties of sorbitol-clarified isotactic polypropylene: Influence of additive concentration on polymer structure and yield behavior
,” Macromolecules
38
, 10461
–10465
(2005
).29.
Kristiansen
, M.
, M.
Werner
, T.
Tervoort
, P.
Smith
, M.
Blomenhofer
, and H. -W.
Schmidt
, “The binary system isotactic polypropylene/bis(3,4-dimethylbenzylidene)sorbitol: Phase behavior, nucleation, and optical properties
,” Macromolecules
36
, 5150
–5156
(2003
).30.
Kühne
, M.
, and C.
Friedrich
, “Nonlinear rheological properties and stability of dibenzylidene sorbitol fiber networks in poly(propylene oxide)
,” Rheol. Acta
48
, 1
–9
(2009
).31.
Lee
, B. -J.
, and S. C.
Jana
, “Strengthening of polyolefins by bottom-up self-assembly of POSS nanoparticles
,” Annu. Pac. Tech. Conf., [Tech. Pap.] (Soc. Plast. Eng.)
66
, 177
–181
(2008
).32.
Lee
, K. M.
, and C. D.
Han
, “Effect of flexible spacer length on the rheology of side-chain liquid-crystalline polymers
,” Macromolecules
36
, 8796
–8810
(2003
).33.
Lee
, Y. -J.
, S. -W.
Kuo
, W. -J.
Huang
, H. -Y.
Lee
, and F. -C.
Chang
, “Miscibility, specific interactions, and self-assembly behavior of phenolic/polyhedral oligomeric silsesquioxane hybrids
,” J. Polym. Sci., Part B: Polym. Phys.
42
, 1127
–1136
(2004
).34.
Leu
, C. -M.
, Y. -T.
Chang
, and K. -H.
Wei
, “Synthesis and dielectric properties of polyimide-tethered polyhedral oligomeric silsesquioxane (POSS) nanocomposites via POSS-diamine
,” Macromolecules
36
, 9122
–9127
(2003
).35.
Mantz
, R. A.
, P. F.
Jones
, K. P.
Chaffee
, J. D.
Lichtenhan
, and J. W.
Gilman
, “Thermolysis of polyhedral oligomeric silsesquioxane (POSS) macromers and POSS-siloxane copolymers
,” Chem. Mater.
8
, 1250
–1259
(1996
).36.
Mercurio
, D. J.
, and R. J.
Spontak
, “Morphological characteristics of 1,3:2,4-dibenzylidene sorbitol/poly(propylene glycol) organogels
,” J. Phys. Chem. B
105
, 2091
–2098
(2001
).37.
Misra
, R.
, B. X.
Fu
, and S. E.
Morgan
, “Surface energetics, dispersion, and nanotribomechanical behavior of POSS/PP hybrid nanocomposites
,” J. Polym. Sci., Part B: Polym. Phys.
45
, 2441
–2455
(2007
).38.
Okada
, A.
, M.
Kawasumi
, A.
Usuki
, Y.
Kojima
, T.
Kurauchi
, and O.
Kamigaito
, “Synthesis and properties of nylon-6/clay hybrids
,” Mater. Res. Soc. Symp. Proc.
171
, 45
–50
(1990
).39.
Park
, J. H.
, and S. C.
Jana
, “The relationship between nano- and micro-structures and mechanical properties in PMMA-epoxy-nanoclay composites
,” Polymer
44
, 2091
–2100
(2003
).40.
Pattanayak
, A.
, and S. C.
Jana
, “Properties of bulk-polymerized thermoplastic polyurethane nanocomposites
,” Polymer
46
, 3394
–3406
(2005a
).41.
Pattanayak
, A.
, and S. C.
Jana
, “Synthesis of thermoplastic polyurethane nanocomposites of reactive nanoclay by bulk polymerization methods
,” Polymer
46
, 3275
–3288
(2005b
).42.
Phillips
, S. H.
, T. S.
Haddad
, and S. J.
Tomczak
, “Developments in nanoscience: Polyhedral oligomeric silsesquioxane (POSS)-polymers
,” Curr. Opin. Solid State Mater. Sci.
8
, 21
–29
(2004
).43.
Pracella
, M.
, D.
Chionna
, A.
Fina
, D.
Tabuani
, A.
Frache
, and G.
Camino
, “Polypropylene-POSS nanocomposites: Morphology and crystallization behavior
,” Macromol. Symp.
234
, 59
–67
(2006
).44.
Ray
, S. S.
, and M.
Okamoto
, “Polymer/layered silicate nanocomposites: A review from preparation to processing
,” Prog. Polym. Sci.
28
, 1539
–1641
(2003
).45.
Scott
, D. W.
, “Thermal rearrangement of branched-chain methylpolysiloxanes
,” J. Am. Chem. Soc.
68
, 356
–358
(1946
).46.
Sellinger
, A.
, and R. M.
Laine
, “Silsesquioxanes as synthetic platforms. Thermally curable and photocurable inorganic/organic hybrids
,” Macromolecules
29
, 2327
–2330
(1996
).47.
Shepard
, T. A.
, C. R.
Delsorbo
, R. M.
Louth
, J. L.
Walborn
, D. A.
Norman
, N. G.
Harvey
, and R. J.
Spontak
, “Self-organization and polyolefin nucleation efficacy of 1,3:2,4-di-p-methylbenzylidene sorbitol
,” J. Polym. Sci., Part B: Polym. Phys.
35
, 2617
–2628
(1997
).48.
Thierry
, A.
, B.
Fillon
, C.
Straupe
, B.
Lotz
, and J. C.
Wittmann
, “Polymer nucleating agents: Efficiency scale and impact of physical gelation
,” Prog. Colloid Polym. Sci.
87
, 28
–31
(1992
).49.
Thierry
, A.
, C.
Straupe
, B.
Lotz
, and J. C.
Wittmann
, “Physical gelation: A path towards ‘ideal’ dispersion of additives in polymers
,” Polym. Commun.
31
, 299
–301
(1990
).50.
Usuki
, A.
, Y.
Kojima
, M.
Kawasumi
, A.
Okada
, Y.
Fukushima
, T.
Kurauchi
, and O.
Kamigaito
, “Synthesis of nylon 6-clay hybrid
,” J. Mater. Res.
8
, 1179
–1184
(1993
).51.
Wilder
, E. A.
, C. K.
Hall
, and R. J.
Spontak
, “Physical organogels composed of amphiphilic block copolymers and 1,3:2,4-dibenzylidene-D-sorbitol
,” J. Colloid Interface Sci.
267
, 509
–518
(2003
).52.
Winter
, H. H.
, “Can the gel point of a cross-linking polymer be detected by the G'–G” crossover?
,” Polym. Eng. Sci.
27
, 1698
–1702
(1987
).53.
Winter
, H. H.
, and F.
Chambon
, “Analysis of linear viscoelasticity of a crosslinking polymer at the gel point
,” J. Rheol.
30
, 367
–382
(1986
).54.
Wu
, J.
, T. S.
Haddad
, G. -M.
Kim
, and P. T.
Mather
, “Rheological behavior of entangled polystyrene-polyhedral oligosilsesquioxane (POSS) copolymers
,” Macromolecules
40
, 544
–554
(2007
).55.
Wu
, J.
, and P. T.
Mather
, “POSS polymers: Physical properties and biomaterials applications
,” Polym. Rev.
49
, 25
–63
(2009
).56.
Xu
, H.
, S. -W.
Kuo
, J. -S.
Lee
, and F. -C.
Chang
, “Glass transition temperatures of poly(hydroxystyrene-co-vinylpyrrolidone-co-isobutylstyryl polyhedral oligosilsesquioxanes)
,” Polymer
43
, 5117
–5124
(2002
).57.
Yamasaki
, S.
, and H.
Tsutsumi
, “Microscopic studies of 1,3:2,4-di-O-benzylidene-D-sorbitol in ethylene glycol
,” Bull. Chem. Soc. Jpn.
67
, 906
–911
(1994
).58.
Yoon
, K. H.
, M. B.
Polk
, J. H.
Park
, B. G.
Min
, and D. A.
Schiraldi
, “Properties of poly(ethylene terephthalate) containing epoxy-functionalized polyhedral oligomeric silsesquioxane
,” Polym. Int.
54
, 47
–53
(2005
).59.
Zeng
, J.
, S.
Kumar
, S.
Iyer
, D. A.
Schiraldi
, and R. I.
Gonzalez
, “Reinforcement of poly(ethylene terephthalate) fibers with polyhedral oligomeric silsesquioxanes (POSS)
,” High Perform. Polym.
17
, 403
–424
(2005
).60.
Zhang
, C.
, and R. M.
Laine
, “Hydrosilylation of allyl alcohol with [HSiMe2OSiO1.5]8: Octa(3-hydroxypropyldimethylsiloxy)octasilsesquioxane and its octamethacrylate derivative as potential precursors to hybrid nanocomposites
,” J. Am. Chem. Soc.
122
, 6979
–6988
(2000
).61.
Zhao
, Y.
, and D. A.
Schiraldi
, “Thermal and mechanical properties of polyhedral oligomeric silsesquioxane (POSS)/polycarbonate composites
,” Polymer
46
, 11640
–11647
(2005
).62.
Zheng
, L.
, R. J.
Farris
, and E. B.
Coughlin
, “Novel polyolefin nanocomposites: Synthesis and characterizations of metallocene-catalyzed polyolefin polyhedral oligomeric silsesquioxane copolymers
,” Macromolecules
34
, 8034
–8039
(2001
).63.
Zheng
, L.
, S.
Hong
, G.
Cardoen
, E.
Burgaz
, S. P.
Gido
, and E. B.
Coughlin
, “Polymer nanocomposites through controlled self-assembly of cubic silsesquioxane scaffolds
,” Macromolecules
37
, 8606
–8611
(2004
).© 2010 The Society of Rheology.
2010
The Society of Rheology
You do not currently have access to this content.
