• Title/Summary/Keyword: solid state polymerization

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Development of Click Chemistry in Polymerization and Applications of Click Polymer

  • Karim, Md. Anwarul
    • Rubber Technology
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    • v.13 no.1
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    • pp.1-9
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    • 2012
  • Click chemistry had enjoyed a wealthy decade after it was introduced by K.B.Sharpless and his co-worker on 2001. Since there is no optimized method for synthesis of click polymer, therefore, this paper introduced three click reaction methods such as catalyst, non-catalyst and azide-end capping for fluorene-based functional click polymers. The obtained polymers have reasonable molecular weight with narrow PDI. The polymers are thermally stable and almost emitted blue light emission. The synthesized fluorene-based functional click polymers were characterized to compare the effect of click reaction methods on polymer electro-optical properties as well as device performance on quasi-solid-state dye sensitized solar cells (DSSCs) applications. The DSSCs with configuration of $SnO_2:F/TiO_2/N719$ dye/quasi-solid-state electrolyte/Pt devices were fabricated using these click polymers as a solid-state electrolyte components. Among the devices, the catalyzed click polymer composed device exhibited a high power conversion efficiency of 4.62% under AM 1.5G illumination ($100mW/cm^2$).These click polymers are promising materials in device application and $Cu^I$-catalyst 1, 3-dipolar cycloaddition click reaction is an efficient synthetic methodology.

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Slug Characteristics in a Bubbling Fluidized Bed Reactor for Polymerization Reaction (기포유동층 고분자 중합 반응기에서의 슬러그 특성)

  • Go, Eun Sol;Kang, Seo Yeong;Seo, Su Been;Kim, Hyung Woo;Lee, See Hoon
    • Korean Chemical Engineering Research
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    • v.58 no.4
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    • pp.651-657
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    • 2020
  • Fluidization processes in which solid particles vividly move like gas or liquid have been widely used in various industrial sectors, such as thermochemical energy conversion and polymerization processes for general purpose polymer resins. One of the general purpose polymer resins, LLDPE(Linear low-density polyethylene) resins have been produced in bubbling fluidized bed processes in the world. In a bubbling fluidization polymerization reactors, LLDPE particles with relatively larger particle size and low density are fluidized by hydrogen gas for polymerization reaction. Though LLDPE polymerization reactors are one of bubbling fluidization processes, slugs that have negative impact for reaction exist or occur in these processes. Therefore, the fluidization state of LLDPE particles was investigated in a simulation model similar to a pilot-scale polymerization reactor (0.38 m l.D., 4.4 m High). In particular, the effect of gas velocity (0.45-1.2 m/s), solid density (900-199 kg/㎥), solid sphericity (0.5-1.0), and average particle size (120-1230 ㎛), on bed height and fluidization state were measured by using a CPFD(Computational particle-fluid dynamics) method. With CPFD analysis, the occurrence of a flat slug was visualized. Also, the change in particle properties, such as particle density, sphericity, and size, could reduce the occurrence of slug and bed expansion.

Effects of Polymerization and Spinning Conditions on Mechanical Properties of PAN Precursor Fibers

  • Qin, Qi-Feng;Dai, Yong-Qiang;Yi, Kai;Zhang, Li;Ryu, Seung-Kon;Jin, Ri-Guang
    • Carbon letters
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    • v.11 no.3
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    • pp.176-183
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    • 2010
  • PAN precursor fibers were produced via wet-spinning process, and effects of polymerization and spinning processes, especially the stretching process, were investigated on mechanical properties and micro-morphologies of precursor fibers. An increase in molecular weight, dope solid and densification and a decrease in surface defects were possible by controlling polymerization temperature, the number of heating rollers for densification and the jet stretch ratio, which improved the mechanical properties of precursor fibers. The curves for strength, modulus, tensile power and diameter as a function of stretch ratio can be divided into three stages: steady change area, little change area and sudden change area. With the increase of stretch ratio, the fiber diameter became smaller, the degree of crystallization increased and the structure of precursor fibers became compact and homogeneous, which resulted in the increase of strength, modulus and tensile power of precursor fibers. Empirical relationship between fiber strength and stretch ratio was studied by using the sub-cluster statistical theory. It was successfully predicted when the strengths were 0.8 GPa and 1.0 GPa under a certain technical condition, the corresponding stretch ratio of the fiber were 11.16 and 12.83 respectively.

Oxidative Coupling Polymerization of Diethynylsilane Derivatives and 1,2-Diethynyl-1,1,2,2-tetramethyldisilane

  • Kim, Ji-Ho;Park, Young-Tae
    • Bulletin of the Korean Chemical Society
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    • v.27 no.6
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    • pp.869-874
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    • 2006
  • We have carried out the Glaser oxidative coupling polymerizations of diethynyldiphenylsilane, diethynylmethylphenylsilane,diethynylmethyloctylsilane, and 1,2-diethynyl-1,1,2,2-tetramethyldisilane to afford polycarbosilanes containing diethynyl and organosilane groups in the main chain, such as poly(diethynyldiphenylsilane), poly(diethynylmethylphenylsilane), poly(diethynylmethyloctylsilane), and poly(1,2-diethynyl-1,1,2,2-tetramethyldisilane), respectively. These obtained materials are almost insoluble in common organic solvents such as $CHCl_3$ and THF probably due to the presence of a rigid rod diacetylene group along the polymer main chain. Therefore, the polymers were characterized using several spectroscopic methods in solid state. FTIR spectra of all the polymeric materials show that the characteristic $C \equiv C$ stretching frequencies appear at 2147-2154 $cm ^{-1}$, in particular. The polymers in the solid state exhibit that the strong maximum excitation peaks appear at 260-283 nm and the strong maximum fluorescence emission bands at 367-412 nm, especially. Thermogravimetric analysis of the materials shows that about 55-68% of the initial polymer weights remain at 400 ${^{\circ}C}$ in nitrogen.

SYNTHESIS OF BLOCK COPOLYMERS CONTAINING POLYPEPTIDE AND ITS BIOMEDICAL APPLICATION

  • Cho, Chong-Su
    • Proceedings of the Korean Society of Sericultural Science Conference
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    • 1997.06a
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    • pp.159-169
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    • 1997
  • ABA-type(or AB) block copolymers composed of poly(${\gamma}$-alkyl L-glutamate) (PALG)[or poly(L-leucine)] as the A component and polyether[or poly (N-isopropy1 acrylamide) as the B component were synthesized by polymerization of (${\gamma}$-alkyl L-glutamate N-carboxyanhydride initiated by primary amined located at both(or one) ends of the polymer chains. Structural studies of the block copolymers were performed in the solution and solid state. Also, artificial skin, drug delivery system of the block copolymers and cell attachment onto the copolymer were carried out for biomedical applications.

The Organization of Nanoporous Structure Using Controlled Micelle Size from MPEG-b-PDLLA Block Copolymers

  • Chang, Jeong-Ho;Kim, Kyung-Ja;Shin, Young-Kook
    • Bulletin of the Korean Chemical Society
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    • v.25 no.3
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    • pp.351-356
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    • 2004
  • Selected MPEG-b-PDLLA block copolymers have been synthesized by ring-opening polymerization with systematic variation of the chain lengths of the resident hydrophilic and hydrophobic blocks. The size and shape of the micelles that spontaneously form in solution are then controlled by the characteristics of the block copolymer template. All the materials prepared in this study showed the tunable pore size of 20-80 ${\AA}$ with the increase of hydrophobic chain lengths and up to 660 $m^2$/g of specific surface area. The formation mechanism of these nanoporous structures obtained by controlling the micelle size has been confirmed using both liquid and solid state $^{13}C\;and\;^{29}Si$ NMR techniques. This work verifies the formation mechanism of nanoporous structures in which the pore size and wall thickness are closely dependent on the size of hydrophobic cores and hydrophilic shells of the block copolymer templates.

Micro-Chemical Structure of Polyaniline Synthesized by Self-Stabilized Dispersion Polymerization

  • NamGoong, Hyun;Woo, Dong-Jin;Lee, Suck-Hyun
    • Macromolecular Research
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    • v.15 no.7
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    • pp.633-639
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    • 2007
  • A variety of NMR techniques were applied to the micro-chemical structural characterization of polyanilines prepared via an efficient synthetic method in a self-stabilized dispersion medium in which the polymerization was conducted in a heterogeneous organic/aqueous biphasic system without any stabilizers. Here, the monomer and growing polymer chain were shown to function simultaneously as a stabilizer, imparting compatibility for the dispersion of the organic phase, and as a form of flexible template in an aqueous reaction medium. Polymerizations predicated on this concept generated polyanilines with a low defect content: solution state $^{13}C-NMR$ and solid $^{13}CDD/CP/MAS$ spectroscopy indicated that the synthesized HCPANi and its soluble derivative, HCPANi-t-BOC, evidenced distinctly different NMR spectra with fewer side peaks, as compared to conventionally prepared PANis, and the complete structural assignments of the observed NMR peaks could be determined via the combination of both 1D and 2D techniques. Ortho-linked defects in HCPANi were estimated to be as low as 7%, as shown by a comparison of the integration of the carbonyl carbon resonance peaks.

Synthesis and Properties of Poly(1,1-diethynyl-1-silacyclopent-3-enes and -1-silacyclobutane)

  • Kim, Eun-Joo;Park, Jung-Woo;Kim, Yong-Rok;Park, Young-Tae
    • Bulletin of the Korean Chemical Society
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    • v.24 no.4
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    • pp.484-488
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    • 2003
  • Polycarbosilanes containing diacetylene and organosilacyclic groups, such as poly(1,1-diethynyl-1-silacyclopent-3-ene), poly(1,1-diethynyl-3-triethylsilyl-1-silacyclopent-3-ene), and poly(1,1-diethynyl-1- silacyclobutane), were synthesized by the Glaser oxidative coupling polymerization reactions of 1,1-diethynyl-1-silacyclopent-3-ene, 1,1-diethynyl-3-triethylsilyl-1-silacyclopent-3-ene, and 1,1-diethynyl-1-silacyclobutane, respectively. These materials are almost insoluble in usual organic solvents such as $CHCl_3$ and THF. The polymers were characterized by using several spectroscopic methods in solid state. FTIR spectra of all the polymeric materials show that the characteristic C≡C stretching frequencies appear at 2146-2170 $cm^{-1}$, in particular. The polymers in the solid state show that the strong maximum excitation peaks appear at 255-257 nm and the strong maximum fluorescence emission bands at 401-402 nm. About 71-87% of the initial polymer weights remain at 400 ℃ in nitrogen according to thermogravimetric analysis.

Synthesis And Ionic Conductivity of Siloxane Based Polymer Electrolytes with Propyl Butyrate Pendant Groups

  • Jalagonia, Natia;Tatrishvili, Tamara;Markarashvili, Eliza;Aneli, Jimsher;Grazulevicius, Jouzas Vidas;Mukbaniani, Omar
    • Korean Chemical Engineering Research
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    • v.54 no.1
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    • pp.36-43
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    • 2016
  • Hydrosilylation reactions of 2.4.6.8-tetrahydro-2.4.6.8-tetramethylcyclotetrasiloxane with allyl butyrate catalyzed by Karstedt's, $H_2PtCl_6$ and Pt/C catalyst were studied and 2.4.6.8-tetra (propyl butyrate)-2.4.6.8-tetramethylcyclotetrasiloxane was obtained. The reaction order, activation energies and rate constants were determined. Ringopening polymerization of 2.4.6.8-tetra (propyl butyrate)-2.4.6.8-tetramethylcyclotetrasiloxane in the presence of $CaF_2$, LiF, KF and anhydrous potassium hydroxide in $60-70^{\circ}C$ temperature range was carried out and methylsiloxane oligomers with regular arrangement of propyl butyrate pendant groups were obtained. The synthesized products were studied by FTIR and NMR spectroscopy. The polysiloxanes were characterized by wide-angle X-ray, gel-permeation chromatography and DSC analyses. Via sol-gel processes of oligomers doped with lithium trifluoromethylsulfonate or lithium bis (trifluoromethylsulfonyl)imide, solid polymer electrolyte membranes were obtained. The dependences of ionic conductivity of obtained polyelectrolytes on temperature and salt concentration were investigated, and it was shown that electric conductivity of the polymer electrolyte membranes at room temperature changed in the range $3.5{\times}10^{-4}{\sim}6.4{\times}10^{-7}S/cm$.