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Synthesis of new type diacetal trioxa-cage compounds via an intramolecular nucleophilic addition of the hydroxy group to the carbonyl oxide group
(1998-10-30)
Wu, HJ
;
Chao, CS
;
Lin, CC
;
應用化學系
;
Department of Applied Chemistry
The synthesis of diacetal trioxa-cage compounds with a new type of skeleton is reported. Ozonolysis of the diols 2a-f, 21, 24, and 33 in CH2Cl2 at -78 degrees C followed by reduction with Me2S gave the diacetal trioxa-cages 3a-f, 22, 25, and 34 in 70-80% yields, respectively. A mechanism via an intramolecular nucleophilic addition of the hydroxy group of the diols to the carbonyl oxide group is proposed for the formation of the diacetal trioxa-cages. The effect of the number of carbon atoms at the bridge of the diols on the formation of the diacetal trioxa-cage skeleton was examined. Ozonolysis of the diols 13 and 15 under the same reaction conditions gave compounds 16 and 18, respectively. No detectable amount of the trioxa-cages 17 and 19 was obtained. For the synthesis of the diacetal trioxa-cages 28a-c and 31, which possess an alkene bond intact, ozonolysis of the diols 27a-c and 30 was performed by controlling the amount of ozone.
An NMR and XRD study of solidification/stabilization of chromium with portland cement and beta-C2S
(1996-06-01)
Lin, CK
;
Chen, JN
;
Lin, CC
;
環境工程研究所
;
材料科學與工程學系
Solidificalion/stabilization of chromium with Portland cement Type I and P-dicalcium silicate (beta-C2S) was investigated by means of the Si-29 solid stale Magic Angle Spinning/Nuclear Magnetic Resonance (Si-29 MAS/NMR) and X-ray Diffraction (XRD) techniques. It is found that chromium nitrate can increase the extent of beta-C2S hydration. It is also confirmed that the chromium ion is easily incorporated into the beta-C2S paste and hydrated Portland cement, and that it affects the characteristics of hydration and hydration products. Formation of beta-calcium chromium oxide hydrate (beta-CaCrO4 . 2H2(O)) during the hydration of chromium-doped beta-C2S and calcium chromium oxide hydrate (CaCrO4 . 2H(2)O) during the hydration of chromium-doped Portland cement indicates the substitution of chromium for silicon in hydration products. The chromium ion, Cr3+, is thus stabilized and solidified through this mechanism.
Characteristics of nonalloyed pseudomorphic high electron mobility transistors using InAs/InxGa1-xAs (x=-> 0) AlyGa1-yAs (y=0 -> 0.3) contact structures
(1997-06-01)
Chen, SS
;
Lin, CC
;
Lan, WH
;
Tu, SL
;
Peng, CK
A molecular beam epitaxy InAs/InxGa1-xAs (x = 1 --> 0)/AlyGa1-yAs (y = 0 --> 0.3) heterojunction was used as an ohmic contact structure to the GaAs-based pseudomorphic high electron mobility transistors (PHEMTs). This nonalloyed PHEMT had a specific contact resistance r(c) of 1.05 x 10(-7) Omega . cm(2) and an extrinsic transconductance g(me) of 272 mS/mm for devices with 1 mu m gate-length, microwave measurements shelved a current gain cut-off frequency f(t) of 22 GHz and a maximum oscillation frequency f(max) of 43 GHz. These results are comparable to our best conventional PHEMTs' alloyed at 450 degrees C and 2 min duration. Meanwhile, a small-signal equivalent circuit model of the nonalloyed PHEMT has also been demonstrated.
Synthesis of novel tetraacetal oxa-cage compounds from 2-methylthiofurans
(1996-04-01)
Lin, CC
;
Huang, FJ
;
Lin, JC
;
Wu, HJ
;
應用化學系
Several novel tetraacetal oxa-cage compounds 9a-9f were synthesized from the corresponding 2-methylthiofurans 1a-1f by a short sequence. The structures of these tetraoxa-cage compounds were deduced from their spectral data and proven by X-ray analysis of 9a. Ozonolysis of the endo adducts 5a-5f in CH2Cl2 at -78 degrees C followed by reduction with dimethyl sulfide gave the tetraoxa-cages 9a-9f in 65-75% yields, respectively. Ozonolysis of the exo adduct 6a under the same reaction conditions gave the tetracarbonyl compound 10. The phenylthio group substituted tetraoxa-cage 13 and the tetraacetal oxa-cage 17, with one more carbon atom on the apex position, were also synthesized in a similar sequence.
Graphical method for the determination of the complex NMR shift and equilibrium constant for a hetero-association accompanying self-associations
(1997-08-01)
Lin, CC
;
Fang, CY
;
Kao, DY
;
Chen, JS
;
應用化學系
We describe a novel graphical method which, in conjunction with the previously proposed graphical determination of mono;ner shift, dimer shift, and dimerization constant for self-association, allows us to determine the complex shift and equilibrium constant for a hetero-association, A + B reversible arrow AB, accompanying self-associations, A + A reversible arrow A(2), and B + B reversible arrow B-2. The merit of the new method includes the removal of the restrictions imposed on the conventional Benesi-Hildebrand (B-H) plot: (1) that the concentration of one component must be much less than that of the other; (2) that there be no accompanying self-association, The simultaneous equilibrium of the self-association of 2-pyrrolidone (A) and that of 4-methyl-alpha-pyrrolidone (B) and the hetero-association between A and B in acetonitrile-d(3) at 25 degrees C is studied. The inappropriateness of the B-H plot in dealing with this case is also pointed out.
Recycling technology of poly(ethylene terephthalate) materials
(1998-12-01)
Lin, CC
;
材料科學與工程學系
;
Department of Materials Science and Engineering
Poly(ethylene terephthalate) (PET) has become one of major post consumer plastics wastes, in addition to polyethylene (PE), polypropylene (PP), polystyrene (PS) and poly(vinyl chloride) (PVC). The challenge to large-volume plastics companies is to team how to collect, separate, reprocess and market their low-cost products and make a profit, too. The effort of. PET recycling, however, is the most successful story in the plastic recycling technology, including both reclaim and upgrade of PET waste. Beverage bottles made of PET are recycled more than 20 % of the total production. The technology of today can reclaim the postconsumer PET bottles to produce high-quality granulated PET with better than 99 % purity. A practical reclaim process for recycling PET bottles (including bottle, HDPE base cup, aluminum cap, liner, label and adhesive) is available by the Center for Plastics Recycling Research in USA. PET recycling process, like for other plastics, can be divided into three categories: incineration, physical recycling, and chemical recycling. To make the plastic recycling business pay requires more than simple recovery and marketing. Greatest profit potential is in upgraded and value-added reclaim products. Upgrading involves compounding with additives to make material more processable, adding reinforcement, or producing extrusions or finished parts from reclaim resins. For instance, a modified injection-moldable resin made from PET bottle scrap is claimed to provide high impact and processability at less cost than competitive materials. It is foreseen that chemical recycling of waste PET bottle becomes feasible if the price of raw material goes up. Three economical processes are involved in this technology: pyrolysis, hydrocracking, and hydrolysis. The hydrolysis process is presently employed to recover the raw material for unsaturated polyester resin manufacture or polyols for the production of polyurethane resin. It is reported in this presentation that polymer concrete could be a huge potential market for chemical reclaim of PET materials, especially for green or mixed-color PET, which are priced lower than colorless PET reclaim materials.
Blends of poly(ethylene terephthalate) with co[poly(ethylene terephthalate-p-oxybenzoate)] .3. Crystallization behavior observed by polarized light microscopy
(1996-08-29)
Ou, CF
;
Lin, CC
;
材料科學與工程學系
;
Department of Materials Science and Engineering
Poly(ethylene terephthalate) (PET) has been melt-mixed at 293 degrees C with two types of co[poly(ethylene terephthalate-p-oxybenzoate)] (POB-PET) copolyester, designated as P28 and P82, at the level of 10 wt %. The different p-acetoxybenzoic acid/PET mole ratios are 20/80 in P28 and 80/20 in P82. The blends were heated to 305 degrees C and then cooled to 25 degrees C at rate of 10 degrees C/min. The crystalline morphology of these blends in the range from 25 degrees C to 305 degrees C is monitored by polarized light microscopy. Morphologic observations revealed a quicker appearance of crystalline in the blends upon the addition of 10 wt % copolyester as a nucleating agent. It is found that P28, which contains fewer POB units, is much more advantageous to the nucleation process than P82, which contains more POB units. According to the optical photomicrographs, sufficient uniformity of distribution of copolyester domains in the PET matrix is reached after 8 min blending. (C) 1996 John Wiley & Sons, Inc.
Synthesis of tetraacetal pentaoxa-cages and convex oxa-cages by ozonolysis of 7-oxabicyclo[2.2.1]heptenes
(1996-06-01)
Lin, CC
;
Wu, HJ
;
應用化學系
;
Department of Applied Chemistry
Tetraacetal pentaoxa-cage compounds 4a and 4b and convex oxa-cage compounds 6, 7 and 8 are synthesized from alkylfurans in three steps. Ozonolysis of the endo adducts 2a and 2b in dichloromethane at - 78 degrees C followed by reduction with dimethyl sulfide gave the tetraacetal pentaoxa-cages 4a and 4b in 85-90% yields, respectively. Ozonolysis of 2a and 2b in dichloromethane at - 78 degrees C followed by treatment with triethylamine gave the convex era-cages 6, 7 and 8 in 85-90% yields, respectively. The synthesis of the tetraacetal pentaoxa-cage 12, possessing aromatic substituents directly on the skeleton of the era-cages, has also been accomplished.
Highly (111) textured titanium nitride layers for sub- quarter-micrometer Al metallization
(1999-07-01)
Wu, WF
;
Lin, CC
;
Huang, CC
;
Lin, HC
;
Chang, TC
Texture improved TiN films were prepared by a two-step deposition process. A thin uncollimated TiN layer is deposited first at low substrate temperature and sputtering power. This layer has poor step coverage and high resistivity, but acts as a crystallographic seed layer for the subsequent collimated TiN layer deposited at high substrate temperature and sputtering power. The TiN layer stack is deposited sequentially without vacuum break. The resulting TiN layer has a low resistivity of 72.25 mu Omega cm, high <111> preferred orientation, and improved bottom coverage in sub-quarter-micrometer contact holes and trenches. (C) 1999 The Electrochemical Society. S1099-0062(99)01-023-8. All rights reserved.
NMR study of hetero-association accompanying self-association of 2-hydroxyl-4-methyl-pyridine and 2-pyrrolidone in acetonitrile
(2000-12-01)
Luo, WC
;
Lin, CC
;
Lin, JA
;
Kao, DY
;
Chen, JS
This work investigated not only the equilibrium of self-association of 2-pyrrolidone (A) and that of 2-hydroxyl-4-methyl-pyridine (B), but also the hetero-association between A and B in [H-2(3)]acetonitrile through hydrogen bonding using high-resolution nuclear magnetic resonance spectroscopy. Dilution shift data for the protons of the NW group of A and OH group of B were measured over a wide range of temperatures and concentrations. In addition, the monomer shifts, dimer shifts and dimerization constants of self-association and hetero-association were evaluated using a graphic method operating on the dilution chemical shift data. The enthalpy and entropy of dimerization of self-association and hetero-association were also obtained from the van't Hoff plot.

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