Synthesis of tetramethyl-p-silphenylenesiloxanedimethylsiloxane triblock copolymer by employing living anionic polymerization

Dimethylsiloxane-tetramethyl-p-silphenylenesiloxane-dimethylsiloxane (DMS-TMPS-DMS) triblock copolymer was synthesized by employing living anionic polymerization of hexamethylcyclotrisiloxane (D₃). Two synthetic methods were carried out for the polymerization. One of those methods was the anionic polymerization of D₃ initiated at the silanolate anion which was prepared from the terminal hydroxyl group of silanol-terminated TMPS prepolymer by reaction with n-butyllithium (method 1). The other was the coupling reaction of vinyl-terminated TMPS prepolymer with hydrosilyl-terminated DMS prepolymer obtained from the anionic polymerization of D₃ by using diphenylmethylsilanolate anion as initiator (method 2). In method 1, DMS contents of the copolymers ranged from 25.8 to 72.5 wt% and the values agreed with the ratio of D₃ to TMPS prepolymer. The weight-average molecular weights ranged from 1.36×10⁴ to 19.4×10⁴ and were close to the predicted values calculated from the $\text{M}\text{?}{}_{\mathrm{v}}$ of the TMPS prepolymer and the amount of D₃ added. In the case of method 2, weight-average molecular weights ranged from 19.5×10⁴ to 24.2×10⁴. The high molecular weight copolymer could thus be obtained by method 2. Intrinsic viscosity values of the triblock copolymers agreed with calculated values obtained by considering the copolymer as a binary mixture of these homopolymers. Differential scanning calorimetry and thermogravimetry were carried out on the triblock copolymers. The equilibrium melting temperatures of each of the copolymers were very close to that of poly-TMPS (160°C). The glass transition temperature and heat of fusion were decreased as the DMS content was increased. The thermogravimetric curves for the copolymers indicated that the thermal stability of the triblock copolymer was intermediate between the DMS and TMPS homopolymers.     

Template synthesis of novel porous carbons using various types of zeolites

As previously reported, high surface area microporous carbons with long-range order can be synthesized by using zeolite Y as a template. In this work, an attempt is made to synthesize porous carbon using several other types of zeolites (zeolite β, ZSM-5, mordenite and zeolite L). Special attention is paid to whether the structural regularity of each zeolite can be transferred to the carbon structure as well as with the case of zeolite Y. The carbon filling method was then examined to see which gives the highest regularity to the carbon structure. It has been found that the optimum carbon filling method for zeolite Y is not an optimum one for the other zeolites and the degree of the regularity of long-range ordering in the carbons strongly depends on zeolite type. The order of the regularity in the resultant carbons is zeolite β>>zeolite L>mordenite>ZSM-5. The effect of zeolite type on the regularity is discussed in relation to the size and the shape of the zeolite channels.     

Antioxidant effects of chlorophyll and pheophytin on the autoxidation of oils in the dark. I. Comparison of the inhibitory effects

The effects of chlorophyll and pheophytin on the autoxidation of oils in the dark were investigated by oven tests. The results indicated that both chlorophyll and pheophytin show antioxidant activity when methyl linoleate is used as substrate. Furthermore, chlorophyll retarded the oxidative deterioration of triglycerides in rapeseed and soybean oils at 30 C. Among the four chlorophyll derivatives (chlorophylls a and b and pheophytins a and b), chlorophyll a showed the strongest antioxidant activity. The antioxidant effects of chlorophyll and pheophytin depended on the storage temperature and the kinds of oil used as substrate.     

Crystalline complex between poly(γ-methyl l-glutamate) and dimethyl phthalate

The crystalline complex between poly(γ-methyl l-glutamate) (PMLG) and dimethyl phthalate (DMP) has been formed in films cast from a solution in dichloroethane. It has the stoichiometry of 1 mol of DMP to three or four residues of PMLG and shows two definite characteristics in X-ray diffraction patterns; one is the large hexagonal unit cell with the edge of around 28 Å and another the ‘extra’ 5.07 Å meridional reflection which can not be interpreted by a PMLG α-helical conformation. The structural examination for the films with various DMP contents is carried out by X-ray, viscoelastic, and d.s.c. measurements and the following structure is proposed for the crystalline complex. Four PMLG are associated to form a group which is hexagonally packed and DMP molecules, located in the gaps between groups, form a specific favourable helical structure along PMLG chains in which the van der Waals stacking of benzene rings of DMP is significant.     

Effect of MgO Addition on the Bondability and Interfacial Reaction between Dielectric and Glass-Ceramics for the Fabrication of Multi-Component Ceramic Substrates

Bondability and interfacial reaction between dielectric and insulator layers have been examined to obtain a basic understanding of bonding mechanisms. Lead-containing complex perovskite was used as a dielectric material. Two kinds of glass-ceramics were used as insulator material; lead borosilicate glass containing Al_2O3 (insulator A) and the same containing Al₂O₃ and M_gO (insulator B). Dielectric and insulator layers did not bond when insulator A was used. When insulator B was used, however, strong bonding was achieved between the two layers by firing the powder compacts at temperatures between 800° and 1000°C. Addition of M_gO to lead borosilicate glass increased the thermal expansion coefficient to that of the dielectric and enhanced the formation of reaction layers, resulting in good bonding. Two reaction layers were identified. The main reaction products were enstatite and bredigite for one layer contacting the dielectric, and enstatite and a compound with the same diffraction pattern as that of faujasite for the other layers contacting insulator B.     

Cationic copolymerization behavior of a bicyclic orthoester having hydroxy group with glycidyl phenyl ether and volume change on their copolymerization

This article describes cationic ring‐opening copolymerization of a bicyclic orthoester having hydroxy group (BOE‐OH) and glycidyl phenyl ether (GPE), and the volume shrinkage behavior during the copolymerization. THF soluble polyethers [poly(BOE‐OH‐co‐GPE)] were obtained by the copolymerizations at 80–180°C, while crosslinked poly(BOE‐OH‐co‐GPE) was obtained by the copolymerizations at 220–250°C. This crosslinking reaction may originate from the dehydration of methylol groups in the side chain of poly(BOE‐OH‐co‐GPE). The volume shrinkage during the cationic copolymerization reduced as the increase of the BOE‐OH feed ratio. By contrast, the volume shrinkage on the crosslinking polymerization was almost independent on the BOE‐OH feed ratio. Poly(BOE‐OH‐co‐GPE)s with higher BOE‐OH composition showed lower thermal weight loss temperature owing to the release of H₂O by dehydration of methylol groups. The BOE‐OH component in the THF soluble poly(BOE‐OH‐co‐GPE)s lowered the glass transition temperature (T_g), while that in the crosslinked poly(BOE‐OH‐co‐GPE) increased the T_g probably because of the higher crosslinking density. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1356–1361, 2006     

Synthesis of poly(tetrahydrofuran-b-ε-caprolactone) macromonomer via the Sml2-induced transformation

Summary A novel well-defined macromonomer consisting of different types of monomers in polymerization mechanisms was synthesized for the first time through the SmI₂-induced transformation. The macromonomer, -methacryloylpoly-(tetrahydrofuran-b--caprolactone), was prepared by the reaction of methacryloyl chloride with living poly(tetrahydrofuran-b--caprolactone) [poly(THF-b-CL)] which was obtained by the two-electron reduction of the cationic growing center of poly(THF) by samarium iodide (SmI₂) followed by the polymerization of CL. ¹H NMR analysis indicated the quantitative introduction of the methacryloyl group onto the polymer end. The molecular weight distribution of the macromonomer was relatively narrow, and the unit ratio of THF to CL could be controlled by both polymerization time of THF and the amount of CL, resulting from the living nature of both CL- and THF-polymerizations. Radical copolymerization of the produced macromonomers with methyl methacrylate in the presence of AIBN resulted in a polymethacrylate backbone grafted with poly(THF-b-CL) block copolymers.     

Rearrangement of the main chain of the organocobalt polymers

The polymers 3 having pyridine moieties in the main chain were synthesized by the reaction of the organocobalt polymers 1 having cobaltacyclopentadiene moieties in the main chain with various nitriles 2. When brown colored 1 and excess 2 were heated in tetrahydrofuran at 80 °C for 24 h and then at 150 °C for 12 h in a sealed tube, the polymers 3 were obtained by the precipitation with methanol in good yields. From the spectroscopic measurements, the resulting polymers 3 were found to contain 35 – 90% of the pyridine moieties depending on the structures of 1. Received: 7 July 1997/Revised: 14 August 1997/Accepted: 25 August 1997     

Oxidation of synthetic triacylglycerols containing eicosapentaenoic and docosahexaenoic acids: Effect of oxidation system and triacylglycerol structure

Thirteen synthetic triacylglycerols (TAG) containing eicosapentaenoic acid (EPA) or docosahexaenoic acid (DHA) were oxidized in the presence of 2,2′-azobis(2,4-dimethyl-valeronitrile) (AMVN) and 2,2′-azobis(2-amidinopropane)dihydrochloride (AAPH) as aqueous and nonaqueous radical initiators to investigate the influence of TAG structure and oxidation system on the oxidative stability of TAG that contain highly unsaturated fatty acids (HUFA). A 2:1 (mol/mol) mixture of trieicosapentaenoylglycerol and tripalmitoylglycerol was most susceptible to the AMVN-initiated oxidation among three types of TAG that contained EPA and palmitic acid (2:1, mol/mol). Compared with 1,2 (or 2,3)-dieicosapentaenoyl-3(or 1)-palmitoylglycerol (EEP) and 1,3-dieicosapentaenoyl-2-palmitoylglycerol (EPE), the oxidative rate of EEP was somewhat higher. A similar result was obtained for DHA-containing TAG. The oxidative rate of TAG that contained EPA and palmitic acid (1:2, mol/mol) showed a positive correlation with the amount of EPA in a single TAG molecule. Moreover, in the nonaqueous system, the oxidative rate of EPA-containing TAG was affected by unsaturation and carbon chainlength of constituent fatty acids. In the AAPH-initiated oxidation in the aqueous system, the oxidative rate of TAG with EPA and palmitic acid was higher with the increased quantity of EPA in a single TAG molecule. Also, constituent fatty acids modified the oxidative rate of EPA-containing TAG in an aqueous system. The glycerol position of EPA and DHA also affected the oxidative rate of the TAG. EPA and DHA located at the 1,2 (or 2,3)-position of glycerol were more oxidizable than those at the 1,3-position during AAPH-initiated oxidation. Thus, 1,2(or2,3)-dipalmitoyl-3(or 1)-eicosapentaenoylglycerol was oxidized faster than 1,3-dipalmitoyl-2-eicosapentaenoylglycerol. These observations suggest that the oxidative stability of TAG that contain HUFA could be modulated by the oxidation system and TAG structure.