Synthesis of organic–inorganic polymer hybrids from poly(vinyl chloride) and polyhedral oligomeric silsesquioxane via CH/π interaction
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Progress in Organic Coatings 64 (2009) 124127
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Progress in Organic Coatings
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Synthe s fand po H/
Takeru Iw ikia Institute for E 26, Japb Department o yo-ku
a r t i c l
Article history:Received 24 JuReceived in reAccepted 18 A
Keywords:Polymer hybriPoly(vinyl chloPolyhedral oligOctaphenethyOctacyclohexyCH/ interacti
60 Cas and. Thof Ph
Synthesis of organicinorganic polymer hybrid material hasattracted mteristic matcan be usorganicinoor inorganicnow, a solto obtain this not neceorganicino
In recen(POSS) hasThe termicate specihydrocarboof silsesquiand partiasilsesquioxapounds candevelopedbased on s
tried utilization of a silsesquioxane as an inorganic compo-nent.
We have recently investigated organicinorganic polymer
0300-9440/$ doi:10.1016/j.puch attention as a preparation method for new charac-erials. Especially, the organicinorganic hybridizationed for the preparation of composite materials ofrganic materials. Moreover, the properties of organicmaterials are reected in the obtained materials. Untilgel reaction has been employed as a general methode organicinorganic polymer hybrids . However, itssary to use a solgel reaction for the preparation ofrganic polymer hybrids.t years, the polyhedral oligomeric silsesquioxanebeen attracting a great deal of attention .
silsesquioxane is the general name for organosil-es with the empirical formulas (RSiO1.5)n (R =H,n) and closely related compounds. The structuresoxanes have been known as irregular, ladder, cage,l cage structures . Since the caged part ofne has similar structure to silica gel, these com-be regarded as an inorganic compound. We have
the synthesis of organicinorganic polymer hybridsilsesquioxanes . However, we have not sufciently
ding author. Tel.: +81 75 383 2604; fax: +81 75 383 2605.ress: firstname.lastname@example.org (Y. Chujo).
hybrids utilizing the weak intermolecular interactions such as interation  and CH/ interaction . In these studies,we succeeded in the preparation of organicinorganic poly-mer hybrids by using the weak intermolecular interactionsbetween the organic polymer and the solgel matrix. For exam-ple, organicinorganic polymer hybrids were prepared utilizingthe CH/ interactions between the CH groups of poly(vinyl chlo-ride) (PVC) and the phenyl groups of solgel matrix which wasderived fromphenyltrimethoxysilane . Therefore,we expect thatorganicinorganic polymer hybrids can be prepared by using theweak intermolecular interactions between the organic polymerand the organic functional groups introduced into the cage-likesilsesquioxanes. In this article, we report on the results of the syn-thesisoforganicinorganicpolymerhybrids fromPVCandcage-likesilsesquioxanes via CH/ interaction (Scheme 1).
Poly(vinyl chloride) (DP=1100) was purchased from Wako PureChemical Industries, Ltd. PVC was puried by reprecipitation fromits THF solution into methanol and dried in vacuo. Octaphenethyl-silsesquioxane (cage mixture, n=8, 10, 12) (Phenethyl-POSS) and
see front matter 2008 Elsevier B.V. All rights reserved.orgcoat.2008.08.035sis of organicinorganic polymer hybridlyhedral oligomeric silsesquioxane via C
amuraa, Kaoru Adachib, Masato Sakaguchia, Yoshnvironmental Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-85f Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishik
e i n f o
ne 2008vised form 15 August 2008ugust 2008
a b s t r a c t
The synthesis of poly(vinyl chloride) (Pwas performed utilizing CH/ interacin THF with octaphenethylsilsesquioxaPOSS) as an inorganic component. Thepolymer hybrid was dried in vacuo atwhen Phenethyl-POSS was employedturbid when Cyclohexyl-POSS was useas an important role for the dispersion/ locate /porgcoat
rom poly(vinyl chloride) interaction
an, Kyoto 615-8510, Japan
olyhedral oligomeric silsesquioxane (POSS) polymer hybridsPoly(vinyl chloride) as an organic component was dissolvedhenethyl-POSS) or octacyclohexylsilsesquioxane (Cyclohexyl-lting mixture was placed at 40 C for 2 weeks. The obtainedfor 2 days. The transparent polymer hybrids were obtainedinorganic component. In contrast, polymer hybrid became
ese results suggest that the CH/ interaction was found to actenethyl-POSS in the PVC matrix.
2008 Elsevier B.V. All rights reserved.
T. Iwamura et al. / Progress in Organic Coatings 64 (2009) 124127 125
octacyclohefrom Sigmasodium andvents and re
Scanningducted usinobtained ongravimetricSEIKO InstrDynamic m(SEIKO Insttemperaturthe rate of 2
2.3. Syntheand silsesqu
PVC (0.5scribed amCyclohexyl-temperatursel coveredThe obtaine
The effesilsesquioxainvestigatedwith Phene
Table 1Synthesis of PV
he resulting mixture was placed at 40 C for 2 weeks. Theed polymer hybrid was dried in vacuo at 60 C for 2 days.ults are summarized in Table 1. Only in the system employ-nethmoved hang powasomaarentand,exyl-t thaof houps aFT-Ire sScheme 1. Synthesis of PVC/R8-P
xylsilsesquioxane (Cyclohexyl-POSS) were purchasedAldrich Co. Tetrahydrofuran (THF) was dried overdistilled under nitrogen atmosphere. The other sol-agents were used as supplied.
electron microscopy (SEM) measurements were con-g a JEOL JSM-5600B system. The FT-IR spectra werea PerkinElmer 1600 infrared spectrometer. Thermo-analysis (TGA) was performed using a TG/DTA6200,uments, Inc., with heating rate of 10 C/min in air.echanical analysis (DMA) was conducted on a DMS 210ruments, Inc.). The sample was measured at 1Hz. Thee for the measurement was raised from 20 to 180 C atC/min.
sis of organicinorganic polymer hybrids from PVCioxane (typical procedure)
nent. TobtainThe resing Pheafter reobtainresultisamplesilica dtranspother hCyclohsuggesthesisCH gro
ThePOSS a0g) was dissolved in 20mL of THF with the pre-ounts of Phenethyl-POSS (0.25g, Table 1, Run 1),POSS (0.25g, Table 1, Run 2). After being stirred at roome for 1h, themixturewas placed in a polypropylene ves-with a wiping paper and left in air at 40 C for 2 weeks.d polymer hybrid was dried in vacuo at 60 C for 2 days.
ct of the organic functional groups introduced to thenes on the homogeneity of polymer hybrid was rst. PVC as an organic component was dissolved in THFthyl-POSS or Cyclohexyl-POSS as an inorganic compo-
C and R8-POSS polymer hybrids.
PVC (g) R8-POSS Appearance
0.501 Phenethyl 0.247 Transparent0.499 Cyclohexyl 0.253 Turbid
Fig. 1. AppeaPVC/Cyclohexyyl-POSS, the transparent polymer hybrid was obtainedalof the solvent (Fig. 1). ThePVC/Phenethyl-POSShybridd good lm forming property. The dispersion in thelymer hybrid was also examined by SEM. When theprepared from Phenethyl-POSS having aromatic rings,
ins could not be found in a micron order. Fig. 2a showspolymer hybrid prepared fromPhenethyl-POSS. On thethe samples prepared from non-aromatic POSS such asPOSS showed phase separation (Fig. 2b). These resultst the CH/ interactions are quite effective for the syn-mogeneous polymer hybrids of polymers having activend the aromatic rings of POSS.R spectra of PVC/Phenethyl-POSS and PVC/Cyclohexyl-hown in Fig. 3. The IR spectrum of PVC showed therance of PVC/Phenethyl-POSS hybrid (Table 1, Run 1) andl-POSS composite (Table 1, Run 2).
126 T. Iwamura et al. / Progress in Organic Coatings 64 (2009) 124127
Fig. 2. SEM images of (a) PVC/Phenethyl-POSS hybrid (Table 1, Run 1) and (b) PVC/Cyclohexyl-POSS composite (Table 1, Run 2).
absorptionquency. Inabsorptionaromatic CHwere shifte3062 cm1)action betwphenethyl gFig. 3. IR spectra of PVC, Phenethyl-POSS, and PVC/Phe
band at 2975 cm1 based on the CH stretching fre-the IR spectrum of PVC/Phenethyl-POSS hybrid, thisband was observed at 2972 cm1. Additionally, thestretching absorption bands at 3106 and 3063 cm1
d to lower frequency after hybridization (3105 and. This result might indicate an existence of CH/ inter-een methine proton adjacent to the chlorine atom androup adjacent to the silicon atom. In the case of the
The dyntigated usinof Phenethyhybrids arecontent, th
Fig. 4. DMA results of PVC/Phenethyl-POSS hybrid: (a) proles of tan versus R8-POSnethyl-POSS hybrid.
hybrid prepared from PVC and Phenethyl-POSS, theg absorption band was shifted to lower frequency aftern.
amic visco-elasticity of the polymer hybrids was inves-g dynamic mechanical analysis to evaluate the effectl-POSS content. The results of DMA for the polymershown in Fig. 4. With an increase in Phenethyl-POSS
e peak temperature of tan and the value of E were
S (wt%) and (b) proles of E versus R8-POSS (wt%).
T. Iwamura et al. / Progress in Organic Coatings 64 (2009) 124127 127
decreased. These results suggest that the hybridization of PVC andPhenethyl-POSS may contribute in weakening the intermolecularinteraction of PVC. As a result, the glass transition temperatureand Youngs modulus of the obtained polymer hybrids might bedecreased.
The hybrid of PVC and polyhedral oligomeric silsesquioxanehaving phenethyl groups was prepared by utilizing the CH/ inter-actions between the CH groups of the organic polymer and thephenethyl groups of POSS. The results show the possibility of thepreparation of the hybrid materials without chemical bonds. Usageof the CH/ interactions may have some advantages in prepara-tionprocess. It canbe incorporated intopreformedorganic polymerwithout modication of the polymers. From the viewpoint of thehybrid preparation,many kinds of hydrophobic polymers are appli-cable to hybridization by using CH/ interaction.
 (a) T. Saegusa, Y. Chujo, J. Macromol. Sci.: Chem. A 27 (13/14) (1990) 16031612;(b) E.M. Ellsworth, B.M. Novak, J. Am. Chem. Soc. 113 (1991) 27562758;
(c) J. Wen, G.L. Wilkes, Chem. Mater. 8 (1996) 16671681;(d) S. Yano, K. Iwata, K. Kurita, Mater. Sci. Eng. C 6 (1998) 7590;(e) T. Ogoshi, Y. Chujo, Compos. Interfaces 11 (2005) 539566.
 (a) F.J. Feher, D.A. Newman, J.F. Walzer, J. Am. Chem. Soc. 111 (1989) 17411748;(b) J.D. Lichtenhan, N.Q. Vu, J.A. Cater, Macromolecules 26 (1993) 21412142;(c) A.T. Tsuchida, C. Bolln, F.G. Sernetz, H. Frey, R. Mlhaupt, Macromolecules 30(1997) 28182824;(d) N.Maxim, P.C.M.M.Magusin, P.J. Kooyman, J.H.M.C. vanWolput, R.A. van San-ten, H.C.L. Abbenhuis, Chem. Mater. 13 (2001) 29582964;(e) J.R. Severn, R. Duchateau, R.A. van Santen, D.D. Ellism, A.L. Spek,Organometallics 21 (2002) 46;(f) A.R. Bassindale, M. Pourny, P.G. Taylor, M.B. Hursthouse, M.E. Light, Angew.Chem. Int. Ed. 42 (2003) 34883490;(g) R. Tamaki, J. Choi, R.M. Laine, Chem. Mater. 15 (2003) 793797;(h) J. Choi, R. Tamaki, S.G. Kim, R.M. Laine, Chem. Mater. 15 (2003) 33653375;(i) J. Choi, A.F. Yee, R.M. Laine, Macromolecules 36 (2003) 56665682.
 R.H. Baney, M. Itoh, A. Sakakibara, T. Suzuki, Chem. Rev. 95 (1995)14091430.
 (a) K.M. Kim, T. Inakura, Y. Chujo, Polym. Bull. 46 (2001) 351356;(b) K.M. Kim, Y. Chujo, J. Polym. Sci. Part A: Polym. Chem. 39 (2001) 40354043;(c) K.M. Kim, K. Adachi, Y. Chujo, Polymer 43 (2001) 11711175;(d) K.M. Kim, D.K. Keum, Y. Chujo, Macromolecules 36 (2003) 867875;(e) K.M. Kim, Y. Ouchi, Y. Chujo, Polym. Bull. 49 (2003) 341348;(f) K.M. Kim, Y. Chujo, J. Polym. Sci. Part A: Polym. Chem. 41 (2003) 13061315;(g) K.M. Kim, Y. Chujo, J. Mater. Chem. 13 (2003) 13841391;(h) K.M. Kim, T. Ogoshi, Y. Chujo, J. Polym. Sci. Part A: Polym. Chem. 43 (2004)473478.
 R. Tamaki, K. Samura, Y. Chujo, Chem. Commun. (1998) 11311132. T. Iwamura, K. Adachi, Y. Chujo, Polym. J. 36 (2004) 871877.
Synthesis of organic-inorganic polymer hybrids from poly(vinyl chloride) and polyhedral oligomeric silsesquioxane via CH/pi interactionIntroductionExperimentalMaterialsMeasurementsSynthesis of organic-inorganic polymer hybrids from PVC and silsesquioxane (typical procedure)
Results and discussionConclusionsReferences