Polybutadiene and hydroxyl terminated polybutadiene (HTPB) were epoxidized using in situ-generated dimethyl dioxirane (DMD) as an oxidant in the presence of nano-TiO2 at 25°C. Reaction time and different percentages of catalyst/Oxone® (w/w) were also examined. The capability of different kinds of double bonds to be epoxidized was studied in detail at various reaction times, and the products were characterized using nuclear magnetic resonance (1HNMR), 13CNMR, and Fourier transform infrared (FT-IR) techniques, with no side reaction being detected. The results indicate that using nano-TiO2 as a catalyst increases the epoxidation yield, especially of cis double bonds.
ChadiriMFarzanehFChandiMAlizadehM. Immobilized copper (II) complexes on montmorillonite and MCM-41 as selective catalysts for epoxidation of alkenes. J Mol Catal A: Chem2005; 233: 127–131.
2.
StenbergBAhlbladGReitbergerTTerseliusB.Thermal oxidation of hydroxyl-terminated polybutadiene rubber I. Chemiluminescence studies. Polym Degrad Stabil1999; 65: 179–184.
3.
GerbaseAEGregorioJRMartinelliMVon HollebenMLAJacobiMAMFreitasLPolymers oxidation with VO (acac)2 complex. Catalysis Today2000; 57: 241–245.
4.
HuangWKHsiueGHHouWH. Epoxidation of polybutadiene and styrene–butadiene triblock copolymers with monoperoxyphthalic acid: Kinetic and conformation study. J Polym Sci Polym Chem Ed1988; 26: 1867–1883.
5.
KoshelNASapunovVNTurovBSPopovaVVUstavshchikovBF. Kinetics and mechanism of epoxidation of low-molecular weight cis-butadiene rubber by tert-butyl hydroperoxide. Polym Sci USSR1980; 22: 2642–2647.
6.
SafferAJohnsonBL. Measurement of Internal Double Bonds in Polymers by Per-benzoic Acid Addition. Ind Eng Chem1948; 40: 538–541.
7.
AguiarMCabral de MenezesSDominguesMacromolL.Configurational double bond selectivity in the epoxidation of hydroxy-terminated polybutadiene with m-chloroperbenzoic acid. Chem Phys1994; 195: 3937–3948.
8.
Martinez-mandezSHenriquesYDominguesOOrnelasLDKrrentzienH. Catalytic properties of silica supported titanium, vanadium and niobium oxide nanoparticles towards the oxidation of saturated and unsaturated hydrocarbons. J Mol Catal A: Chem2006; 252: 226–234.
9.
JianXHayAS. Epoxidation of unsaturated polymers with hydrogen peroxide. J Polym Sci Pol Lett1990; 28: 285–288.
10.
KachasakulPAssabumrungratSPraserthdamPPancharoenU. Extractive reaction for epoxidation of cyclohexene to cyclohexene oxide using dioxirane in ketone/Oxone® system. Chem Eng J2003; 92: 131–139.
11.
Brown RipinDHCaiWBrenekSJ. A safe, scaleable method for the oxidation of carbon–boron bonds with Oxone. Tetrahedron Lett2000; 41: 5817–5819.
12.
ZhangWLoebachJLWilsonSRJacobsenEN. Enantioselective epoxidation of unfunctionalized olefins catalyzed by salen manganese complexes. J Am Chem Soc1990; 112: 2801–2803.
13.
KureshyRIKhanNHAbdiSHRIyerPABhattK. Enantioselective catalytic epoxidation of nonfunctionalized prochiral olefins by dissymmetric chiral Schiff base complexes of Mn (III) and Ru (III) metal ions. J Mol Catal A: Chem1997; 120: 101–108.
14.
TraylorTGMiksaztalR. Alkene epoxidations catalyzed by iron (III), manganese (III) and chromium (III) prophyrins. J Am Chem Soc1989; 111: 7443–7448.
15.
FranklinCCVanAttaRBTaiAFValentineJS. Copper ion mediated epoxidation of olefins by iodosylbenzene. J Am Chem Soc1984; 106: 814–816.
16.
TaiAFMargerumLDValentineJS. Epoxidation of olefins by iodosylbenzene catalyzed by binuclear copper (II) complexes. J Am Chem Soc1986; 108: 5006–5008.
17.
NamWValentineJS. Zinc (II) complexes and aluminum(III) porphyrin complexes catalyze the epoxidation of olefins by iodosylbenzene. J Am Chem Soc1990; 112: 4977–4979.
18.
YangWDiederichFValentineJS. Lewis acidic catalysts for olefin epoxidation by iodosylbenzene. J Am Chem Soc1991; 113: 7195–7205.
19.
Alavi NikjeMMRafieeAHaghshenasM. Epoxidation of polybutadiene using in situ generated dimethyl dioxirane (DMD) in the presence of tetra-n-butyl ammonium bromide. Des Monomers Polym2006; 9: 293–303.
20.
Alavi NikjeMMMozaffariZ. Chemoselective epoxidation of hydroxyl-terminated polybutadiene (HTPB) using in-situ generated dimethyl dioxirane (DMD). Des Monomers Polym2007; 10:67–77.
21.
Alavi NikjeMMMozaffariZ. Selective epoxidation of hydroxyl terminated polybutadiene using in situ generated dimethyl dioxirane in the presence of MoO3. Polymer2007; 52: 28–34.
22.
Alavi NikjeMMMozaffariZ. Polybutadiene and Hydroxyl Terminated Polybutadiene Epoxidation Using In Situ-Generated Dimethyl Dioxirane (DMD)/Transition Metal Salts Complex. Des Monomers Polym2008; 11: 271–281.
23.
Alavi NikjeMMMozaffariZ.In situ Generated Dimethyl Dioxirane (DMD)/Copper (II) (2,2-diamino-4,4-bithiazole) Complex as a New Oxidant for Polybutadiene and Hydroxyl Terminated Polybutadiene (HTPB) Epoxidation. J Elastomers Plast2009; 41: 41–64.
24.
Alavi NikjeMMHajifathealiH. Nanoclay-Mediated Epoxidation of HTPB Using In-Situ Generated Dimethyl Dioxirane. Des Monomers Polym2011; 14: 155–165.
25.
TengvallPElwingHSjogvistLLundstroemIBjurstenM.Interaction between hydrogen peroxide and titanium: A possible role in the biocompatibility of titanium. Biomaterials1989; 10: 118–120.
26.
RagaiJ. Trapped radicals in titania gels. Nature1987; 325: 703–705.
27.
TengvallPWaölivaaraBWesterlingJLundströmI. Stable titanium superoxide radicals in aqueous Ti-peroxy gels and Ti-peroxide solutions. J Colloid Interface Sci1991; 143: 589–592.
28.
DewkarGKNikaljeMDAliISParaskarASJagtapHSSudalaiA.An Exceptionally Stable Ti Superoxide Radical Ion: A Novel Heterogeneous Catalyst for the Direct Conversion of Aromatic Primary Amines to Nitro Compounds. Angew Chem Int Ed2001; 40: 405–408.
29.
GotoHHanadaYOhnoTMatsumuraM. Quantitative analysis of superoxide ion and hydrogen peroxide produced from molecular oxygen on photoirradiated TiO2 particles. J Catal2004; 225: 223–229.
30.
KanezakiESakamotoTOokuboAOoiK.Solid-state chemistry of thermally induced yellow colouring in synthetic hydrous titanium oxide from TiCl3. J Chem Soc Faraday Trans1992; 88: 3583–3586.
31.
SrinivasDManikandanPLahaSCKumarRRatnasamyP.Reactive oxo-titanium species in titanosilicate molecular sieves: EPR investigations and structure–activity correlations. J Catal2003; 217: 160–171.
32.
ShettiVNManikandanPSrinivasDRatnasamyP. Reactive oxygen species in epoxidation reactions over titanosilicate molecular sieves. J Catal2003; 216: 461–467.
33.
ChaudhariKSrinivasDRatnasamyP.Reactive Oxygen Species in Titanosilicates TS-1 and TiMCM-41: An In Situ EPR Spectroscopic Study. J Catal2001; 203: 25–32.
34.
ClericiMIngallinaP. Epoxidation of lower olefins with hydrogen peroxide and titanium silicalite. J Catal1993; 140: 71–83.
35.
NiedererJPMHolderichWF. Oxidation capabilities of BEA isomorphously substituted with molybdenum, vanadium and titanium: an explorative study. Appl Catal A: Gen2002; 229: 51–64.
36.
TuelAHubert-PfalzgrafLG.Nanometric monodispersed titanium oxide particles on mesoporous silica: synthesis, characterization, and catalytic activity in oxidation reactions in the liquid phase. J Catal2003; 217: 343–353
37.
HutterRMallatTBaikerA. Titania-Silica Mixed Oxides: III. Epoxidation of α-Isophorone with Hydroperoxides. J Catal1995; 157: 665–675.
38.
KanaiHIkedaYImamuraS. Epoxidation of allyl acetate with tert-butyl hydroperoxide catalyzed by MoO3/TiO2. Appl Catal A: Gen2003; 247: 185–191.
39.
TalsiEPBabushkinDE. Nature of the reactive intermediates from the titanium-induced activation of hydrogen peroxide: Studies using 1H and 17ONMR. J Mol Catal1996; 106: 179–185.
40.
RamaswamyVAwatiPRamaswamyAV. Epoxidation of indene and cyclooctene on nanocrystalline anatase titania catalyst. Top Catal2006; 38: 251–259.
41.
AdamWHadjiarapoglouHL.Dimethyldioxirane epoxidation of α,β-unsaturated ketones, acids and esters. Tetrahedron Lett1990; 31: 331–334.
42.
GemmerRVGolubMA. 13CNMR spectroscopic study of epoxidized 1,4-polyisoprene and 1,4-polybutadiene. J Polym Sci1978; 16: 2985–2990.
43.
ZuchowskaD.Polybutadiene modified by epoxidation. 1. Effect of polybutadiene microstructure on the reactivity of double bonds. Polymer1980; 21: 514–520.
44.
NazareANDeuskarVDAsthanaSNShrotriPG. Influence of characteristics of HTPB on mechanical properties and ballistic behavior of composite propellant. J Polym master1993; 10: 213–215.
