• Title/Summary/Keyword: polymerization reaction

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A Study on the Emulsion Polymerization of Methyl Methacrylate (Methyl Methacrylate의 Emulsion Polymerization에 關한 硏究)

  • Lee, Hyung-Kyoo;Min, Tae-Ik
    • Journal of the Korean Chemical Society
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    • v.12 no.1
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    • pp.4-11
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    • 1968
  • With the selected emulsifiers for the emulsion polymerization of methyl methacrylate, the HLB of the emulsifier in the reaction system has been studied on the effect of the ratio of tetra sodium-N-(1,2-dicarboxy ethyl)-N-octadecyl sulfosuccinamate(Aerosol 22) to polyethylene glycol nonyl phenyl ether (Noigen EA 160), and also sodium lauryl sulfate(Quolac EX-UB), Disodium-N-octadecyl sulfosuccinamate (Aerosol 18) and Aerosol 22 as emulsifiers having various hydrophilic groups in the molecules have been studied. Results are as follows; 1) The viscosity of the emulsions and the molecular weight of the polymers have maximum values at a constant HLB value of emulsifiers, but their stabilities show minimum point at the value with the titration with the three kinds of mono, bi, tri-valent electrolytes. These results are agreed on the theory of Greth & Wilson in which the properties of polymer emulsions depend upon the HLB system of emulsifiers. 2) The viscosity of the emulsions and the molecular weights of the produced polymers increase more in the case of blending of Aerosol 22 to Noigen EA-160 than of the separate using. 3) The coagulation effects of the divalent electrolytes($ex,\;Ca^{++},\;Zn^{++}$) are contrast to the effects of monovalent($ex,\;Na^+$) and trivalent($ex,\;Al^{+++}$) in the emulsions with Aerosol 18 or Aerosol 22 which have more than two hydrophilic groups. It seems that the stability of the O/W emulsions by electrolytes is directly related to the parameters of surface physical chemistry such as surface geometry of surface chemical constitution of polymer particles.

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Ring-Opening Metathesis Polymerization and Hydrogenation of Ethyl-substituted Tetracyclododecene

  • Kwon, Oh-Joon;Vo, Huyen Thanh;Lee, Sul-Bee;Kim, Tae-Kyung;Kim, Hoon-Sik;Lee, Hyun-Joo
    • Bulletin of the Korean Chemical Society
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    • v.32 no.8
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    • pp.2737-2742
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    • 2011
  • Ring-opening metathesis polymerization (ROMP) of an ethyl-substituted tetracyclododecene (8-ethyltetracyclo[$4.4.0.1^{2,5}.1^{7,10}$] dodec-3-ene, Et-TCD) was carried out in the presence of a ternary catalyst system consisting of $WCl_6$, triisobutyl aluminium (iso$Bu_3Al$), and ethanol. The optimal molar ratio of Et-TCD/$WCl_3$/iso-$Bu_3Al$/ethanol was found as 500/1/3/2 at which the yield of ring-opened polymer was 100%. 1-Hexene was shown to be an effective molecular weight controlling agent for ROMP reaction of Et-TCD. The hydrogenation of the ring opened polymer (p-Et-TCD) was conducted successfully using Pd(5 wt %)/${\gamma}$-$Al_2O_3$ at $80^{\circ}C$ for 1 h. Chemical structures of p-Et-TCD and its hydrogenated product($H_2$-p-Et-TCD) were characterized using 2D NMR techniques ($^1H-^1H$ COSY and $^1H-^{13}C$ HSQC). The changes of physical properties such as thermal stability, glass transition temperature and light transmittance after the hydrogenation were also investigated using TGA, DSC, and UV.

Study of Emulsion Polymerization Condition of Aqueous Adhesive (유화중합을 이용한 수분산성접착제의 중합조건에 관한 연구)

  • Lee, HaengJa;Park, JiSun;Lee, SangRok;Kim, JongMin;Chang, SangMok
    • Korean Chemical Engineering Research
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    • v.47 no.4
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    • pp.470-475
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    • 2009
  • To study the optimal synthesis conditions of aqueous acrylic adhesive using emulsion polymerization, the effects of monomer, surfactant and initiator on the adhesive properties, such as conversion rate, particle size, peel strength, and glass transition temperature, were investigated. 2-EHA, n-BA and MMA were used as main monomers, 2-HEMA and AAc as functional monomers, SLS as surfactant and APS as initiator, respectively. The conversion rate was over 95% at 3.75% surfactant(SLS/monomer), 0.612% initiator(APS/monomer) and $82^{\circ}C$ reaction temperature. When the excess amount of surfactant or initiator was used, the peel strength represented decreasing tendency. The maximum conversion rate and peel strength were obtained at 65% 2-EHA/monomer, 20% BA/monomer, and 10% MMA/monomer.

Synthesis, chemically and electrochemically polymerization of N-substituted pyrrole containing azo chromophore and its copolymerization with pyrrole

  • Hosseini, Seyed Hossein
    • Advances in materials Research
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    • v.1 no.4
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    • pp.299-310
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    • 2012
  • This article describes the synthesis of a novel N-substituted pyrrole monomer containing an azobenzene group. The 2-[N-ethyl-N-[4-[(4-nitrophenyl) azo]-phenyl] amino] ethyl-3-chloropropionate (RedII) compound was synthesized via reaction of 4-nitro-4'-[N-ethyl-N-(2-hydroxyethyl)-amino] azobenzene (RedI) and 3-chloropropionic acid. RedII was reacted with the potassium salt of pyrrole then 2-[N-ethyl-N-[4-[(nitro phenyl) azo] phenyl] amino] ethyl-N-pyrrolyl propionate (Py-RedII) was prepared. Chemical polymerization of Py-RedII and copolymerization of Py-RedII with pyrrole carried out using $FeCl_3$. Poly (2-[N-ethyl-N-[4-[(nitro phenyl) azo] phenyl] amino] ethyl-N-pyrrolyl propionate) (PPy-RedII) was characterized by UV, IR, $^1HNMR$, $^{13}CNMR$ spectroscopies. Electropolymerization of Py-RedII and electroco-polymerization of Py-RedII and pyrrole were studied using conventional three electrodes system, Ag/AgCl reference electrode, platinum counter electrode and GC disk working electrode. Scanning electron microscopy (SEM), thermogravimetry analysis (TGA) and differential scanning calorimetry (DSC) were used for thermal and rheological studies. The TGA curve of PPy-RedII demonstrated a high thermal stability up to 200°C and its DSC thermogram showed two endothermic peaks at 88 and $122^{\circ}C$. The glass transition temperature of the polymer was found to be above the room temperature. Electrical conductivities of PPy-RedII and it's copolymer with pyrrole (PPy-RedII-co-Py) were studied by the four-probe method and produced conductivities of $7.5{\times}10^{-4}$ and $6.5{\times}10^{-3}Scm^{-1}$, respectively.

Theoretical Studies on The Cationic Polymerization Mechanism of Oxetanes (산촉매하의 옥세탄 공중합에 관한 분자 궤도론적 연구)

  • Cheun, Young-Gu;Kim, Joon-Tae;Park, Seong-Kyu
    • Journal of the Korean Chemical Society
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    • v.35 no.6
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    • pp.636-644
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    • 1991
  • The cationic polymerization of substituted oxethanes which have pendant energetic groups such as methoxy, azido, and nitrato are investigated theoretically using the semiempirical MINDO/3, MNDO, and AM1 methods. The nucleophilicity and basicity of substituted oxethanes can be explained by the negative charge on oxygen atom of oxetanes. The reactivity of propagation in the polymerization of oxetanes can be represented by the positive charge on carbon atom and the low LUMO energy of active species of oxetanes. The reaction of the energetic cyclic oxonium ion forms to the open chain carbenium ion forms is expected by computational stability energy of the oxonium and carbenium ion (about 10~20 kcal/mole) favoring the carbenium ion. The relative equilibrium concentration of cyclic oxonium and open carbenium ions is found to be a major determinant of mechanism, owing to the rapid equilibrium of these cation forms and the expectation based on clauclation that the prepolymer propagation step SN1 mechanism will be at least as fast as that for SN2 mechanism.

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Degradation Characteristics of Ligninsulfonate by Laccase and Mn-peroxidase (Laccase와 Mn-peroxidase에 의한 Ligninsulfonate의 분해 특성)

  • Bae, Hyeun-Jong;Kim, Yoon-Soo;Mun, Sung-Phil
    • Journal of the Korean Wood Science and Technology
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    • v.23 no.4
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    • pp.27-32
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    • 1995
  • To understand whether ligninolytic enzyme catalyze polymerization or depolymerization of the high molecular weight (HMW) lignin, the action of laccase and Mn-peroxidase (MnP) towards commercial ligninsulfonates (LS) was examined in various conditions of pH and cosubstrates. Polymerization occurred when LS was incubated with laccase at pH 6.0. In contrast, the high molecular weight portions were significant1y reduced at pH 4.5, especially when glucose was added. When LS was treated with MnP at pH 4.5, compounds of low molecular weight were produced. In particular, when cellobiose was added to Mn-P reaction mixture, the breakdown of LS was observed. In conclusion, degradation of LS by laccase and MnP occurred primarily at pH 4.5 where-as polymerization of LS was dominant at pH 6.0. Color index, however, was not greatly changed in the degradation mixtures of LS.

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Synthesis and Characterization of Allyl Ester Resin-Layered Silicate Nanocomposite (알릴 에스터 수지-층상 실리케이트 나노복합재료의 합성과 특성)

  • 팽세웅;김장엽;허완수;조길원;이상원
    • Polymer(Korea)
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    • v.28 no.2
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    • pp.177-184
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    • 2004
  • Polymer-clay nanocomposite containing the low amounts of clay shows improved physical, mechanical properties. In this study, allyl ester prepolymer was synthesised by reactions of the diallyl terephthalate monomers and the 1,3-butanediol monomers. Nanocomposites of allyl ester prepolymer and the two kinds of the organically layered silicate were prepared by using the intercalation method as well as the in-situ polymerization method using. By varying the amount of clay content, curing conditions, and feeding conditions. the nanocomposite was studied using X-ray diffraction. From XRD results, allyl ester-Cloisite 30 B nanocomposite made by the in-situ polymerization method shows better exfoliation behavior compared with the intercalation method. It can be said that the transesterification reaction between functional groups (-OH) of intercalant and monomers results in the increased gallery distance. Also mechanical and thermal properties indicate that the dispersity of clay is an important factor for improving physical properties of the nanocomposite.

Phenol Removal Using Horseradish Peroxidase(HRP)-Mediated Polymerization Reaction in Saturated Porous Media (다공성 포화 매질에서 효소 중합반응을 이용한 페놀 제거)

  • Kim, Won-Gee;Lee, Seung-Mok
    • Journal of Korean Society of Environmental Engineers
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    • v.30 no.10
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    • pp.984-991
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    • 2008
  • This paper reports experimental results, demonstrating the feasibility of horseradish peroxidase(HRP) and H$_2$O$_2$ to reduce phenol transport in saturated porous media. A laboratory-scale packed column reactor(ID: 4.1 cm, sand-bed height 12 cm) column was utilized to simulate injection of HRP and H$_2$O$_2$ into an aquifer contaminated with phenol. Effluent concentrations of phenol and polymerization products were monitored before and after enzyme addition under various experimental conditions(enzyme dose: 0$\sim$2 AU/mL, [ionic strength]: 5$\sim$100 mM, pH: 5$\sim$9). The concentration of phenol in the column effluent was found to decrease by nearly 90% in the presence of HRP(2 AU/mL) and H$_2$O$_2$ in the continuous flow system at pH 7 and ionic strength 20 mM. The influent phenol was converted in the system to insoluble precipitate, which deposited in pore spaces. The remains were discharged as soluble oligomers. About 8% of total pore volume in column system was decreased by deposition of polymer produced.

Ring-Opening Polymerization of $\varepsilon$-Caprolactone and Cyclohexene Oxide Initiated by Aluminum $\beta$-Ketoamino Complexes: Steric and Electronic Effect of 3-Position Substituents of the Ligands

  • Liu, Binyuan;Li, Haiqing;Ha, Chang-Sik;Kim, Il;Yan, Weidong
    • Macromolecular Research
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    • v.16 no.5
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    • pp.441-445
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    • 2008
  • A series of aluminum complexes supported by $\beta$-ketoamino, ligand-bearing, 3-position substituents $LAlEt_2$ ($L=CH_3C(O)C(Cl)=C(CH_3)NAr\;(L_1)$, $L=CH_3C(O)C(H)=C(CH_3)NAr\;(L_2)$, $L=CH_3C(O)C(Ph)=C(CH_3)NAr\;(L_3)$, and $L=CH_3C(O)C(Me)=C(CH_3)NAr\;(L_4)$, $Ar=2,6-^iPr_2C6H_3$) were synthesized in situ and employed in the ring-opening polymerization (ROP) of $\varepsilon$-caprolactone ($\varepsilon$-CL) and cyclohexene oxide (CHO). The 3-position substituents on the $\beta$-ketoamino ligand backbone of the aluminum complexes influenced the catalyst activity remarkably for both ROP of $\varepsilon$-CL and CHO. Aluminum $\beta$-ketoamino complexes displayed different catalytic behavior in ROP of $\varepsilon$-CL and CHO. The order of the catalytic activity of $LAlEt_2$ was $L_1AlEt_2$>$L_2AlEt_2$>$L_3AlEt_2$>$L_4AlEt_2$ for ROP of $\varepsilon$-CL, being opposite to the electron-donating ability of the 3-position substituents on the $\beta$-ketoamino ligand, while the order of the catalytic activity for ROP of CHO was $L_1AlEt_2$>$L_3AlEt_2$>$L_4AlEt_2$>$L_2AlEt_2$. The effects of reaction temperature and time on the ROP were also investigated for both $\varepsilon$-CL and CHO.

Orientational Control of Nano Structures from Block Copolymer Using Homo-Polymer Nano Interface (단일 성분 고분자 나노 계면의 도입을 통한 블락 고분자 박막의 나노 구조 배향 조절)

  • In, Insik
    • Journal of Adhesion and Interface
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    • v.9 no.4
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    • pp.30-33
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    • 2008
  • Two polymeric interfaces with single component homo-polymers were prepared to control the orientation of block copolymer thin-film nanostructures. Poly(4-acetoxy styrene) (OH-PAS) and poly(4-methoxy styrene) (OH-PMS) which have the average chemical composition of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) were precisely synthesized through nitroxide-mediated radical polymerization. After dehydration reactions between above polymers and SiOx layers of silicon wafers, the polymer-modified interface induced partial (30%) vertical orientation of PS-b-PMMA thin film in the case of OH-PMS and wholly parallel orientation in the case of OH-PAS. Chemical compositions of polymeric interface layers are regarded as the key parameter to control the orientation of nanostructures of block copolymer thin film.

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