• Macromolecular Research
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• v.10 no.6
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• pp.339-344
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• 2002

Poly(vinyl alcohol-b-styrene) (poly(VA-b-St)) diblock copolymer containing high syndiotactic poly (vinyl alcohol) (PVA) was synthesized by the saponification of poly(vinyl pivalate-b-styrene) (poly(VPi-b-St)). For the block copolymer, poly(vinyl pivalate) (PVPi) with trichloromethyl end group was obtained via telomerization of vinyl pivalate with carbon tetrachloride as a telogen and 2,2-azobisisobutyronitrile (AIBN) as an initiator. Then resulting poly(vinyl pivalate) with trichloromethyl end group was used as an effient macroinitiator for the synthesis of poly(VPi-b-St) using atom transfer radical polymerization (ATRP) in the presence of CuCl/2,2'-bipyridine at 130 $^{\circ}C$. The poly(vinyl pivalate) macroinitiator, poly(VPi-b-St), poly(VA-b-St) were characterized by GPC, FT-IR and $^1$H-NMR. And the analysis showed that integrity of the block copolymer was maintained during saponification reaction.

• Textile Coloration and Finishing
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• v.7 no.4
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• pp.45-53
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• 1995

Natural rubber(NR)-polyacrylamide(PAAm) graft copolymers(GP)(toluene soluble GP : TSGP, water dispersible GP : WDGP) have been synthesized as coupling agents by pre-emulsification methods based on "inverse emulsion graft polymerization" technique. The polymerization was carried out at $65^{\circ}C$ using Azobisisobytyro nitrile(AIBN) as an initiator in the inverse emulsion system formed by inxing NR toluene solution with inverse emulsion of awueous AAm solution emulsified with $Tween^{\#}$ 80 in toluene. The mechanism of inverse emulsion graft copolymerization was studied on AAm conversion, % grafting, grafting efficiency, NR conversion, production ratio of TSGP and amount of GP(sum of TSGP and WDGP). The reaction has been confirmed through use of optical microscope to proceed via adsorption of emulsifier colloid particles onto the stretched NR molecule. From the analysis of the effects of various polymerization conditions on the grafting, it has also been found that the present rection system can easily yield high(over 90%) grafting efficiency and AAm conversion and relatively high(over 80%) NR conversion.onversion.

• Restorative Dentistry and Endodontics
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• v.24 no.2
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• pp.265-285
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• 1999

The purposes of this investigation were to observe the reaction kinetics of five commercial dual cured resin cements (Bistite, Dual, Scotchbond, Duolink and Duo) when cured under varying thicknesses of porcelain inlays by chemical or light activation and to evaluate the effect of the porcelain disc on the rate of polymerization of dual cured resin cement during light exposure by using thermal analysis. Thermogravimetric analysis(TGA) was used to evaluate the weight change as a function of temperature during a thermal program from $25{\sim}800^{\circ}C$ at rate of $10^{\circ}C$/min and to measure inorganic filler weight %. Differential scanning calorimetry(DSC) was used to evaluate the heat of cure(${\Delta}H$), maximum rate of heat output and peak heat flow time in dual cured resin cement systems when the polymerization reaction occured by chemical cure only or by light exposure through 0mm, 1mm, 2mm and 4mm thickness of porcelain discs. In 4mm thickness of porcelain disc, the exposure time was varied from 40s to 60s to investigate the effect of the exposure time on polymerization reaction. To investigate the effect on the setting of dual cured resin cements of absorption of polymerizing light by porcelain materials used as inlays and onlays, the change of the intensity of the light attenuated by 1mm, 2mm and 4mm thickness of porcelain discs was measured using curing radiometer. The results were as follows 1. The heat of cure of resin cements was 34~60J/gm and significant differences were observed between brands (P<0.001). Inverse relationship was present between the heat of reaction and filler weight % the heat of cure decreased with increasing filler content (R=-0.967). The heat of reaction by light cure was greater than by chemical cure in Bistite, Scotchbond and Duolink(P<0.05), but there was no statistically significant difference in Dual and Duo(P>0.05). 2. The polymerization rate of chemical cure and light cure of five commercially available dual cured resin cements was found to vary greatly with brand. Setting time based on peak heat flow time was shortest in Duo during chemical cure, and shortest in Dual during light cure. Cure speed by light exposure was 5~20 times faster than by chemical cure in dual cured resin cements. The dual cured resin cements differed markedly in the ratio of light and chemical activated catalysts. 3. The peak heat flow time increased by 1.51, 1.87, and 3.24 times as light cure was done through 1mm, 2mm and 4mm thick porcelain discs. Exposure times recommended by the manufacturers were insufficient to compensate for the attenuation of light by the 4mm thick porcelain disc. 4. A strong inverse relationship was observed between peak heat flow and peak time in chemical cure(R=0.951), and a strong positive correlations hip was observed between peak heat flow and the heat of cure in light cure(R=0.928). There was no correlationship present between filler weight % or heat of cure and peak time. 5. The thermal decomposition of resin cements occured primarily between $300^{\circ}C$ and $480^{\circ}C$ with maximum decomposition rates at $335^{\circ}C$ and $440^{\circ}C$.

• Polymer(Korea)
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• v.35 no.1
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• pp.66-71
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• 2011

With the synthesis of hyper crosslinked polymer particle (HCPP), having microporous structure with hydroxyl functional group, synthesized via polymerization reaction consists of three stepssuspension polymerization, hyper crosslinking by Friedel-Craft catalysis and hydrolysis reaction, the effects of the ratio of each monomer, hyper crosslinking conditions and $CO_2$ supercritical drying on the variations of surface morphology, pore size & distribution and BET surface area of HCPP have been investigated. It was observed that the formation of surface crack or fracture of HCPP was intimately related with the degree of hyper crosslinking reaction between microphase separated domains. And the value of BET surface area of HCPP increased with the increase of reaction temperature, time and the amounts of solvent used in hyper crosslinking step. Moreover, $CO_2$ supercritical drying was proven to be a very effective method for removing stabilizer, unreacted monomers and oligomers from HCPP but needed to add methanol as a co-solvent for efficient removing of residual catalyst.

• Journal of the Korean Society of Propulsion Engineers
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• v.18 no.5
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• pp.35-42
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• 2014

Thermal analysis properties and adhesive properties of self-healing agents were evaluated through differential scanning calorimetry, reaction heat measurement, and adhesive shear test. D1E0, D3E1, D1E1, D1E3, and D0E1, depending on the mixing ratio of DCPD and ENB, were considered as self-healing agents. The amount of Grubbs' catalyst, depending on the type of self-healing agents, was varied from 0.1 wt% to 1.5 wt%. In the case of DCPD, the polymerization reaction occurred faster and the stabilized adhesive strength increased as the amount of catalyst increased; however, a large amount of catalyst was required. ENB had excellent reactivity with a small amount of the catalyst; however, high reaction heat was observed at the early stage of polymerization. Thermal analysis properties and adhesive properties of self-healing agents can be controlled by varying a mixing ratio of DCPD and ENB. Among the self-healing agents used for this study, the D3E1 would be one of the most preferable candidates with regard to maximum adhesive strength, reaching time to maximum adhesive strength, stabilized adhesive strength, and reaction heat.

• Applied Chemistry for Engineering
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• v.5 no.2
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• pp.313-320
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• 1994

Rosin-maleic anhydride adduct(RMA) was synthesized from rosin and maleic anhydride. Highly purified RMA for the application of polymerization monomer was synthesized by means of two methods; the melt reaction followed by further purification and the solution reaction. As a result of this study, the solution reaction was better than the melt reaction for obtaining higher yield of RMA. Maximum yield of RMA obtained by the melt reaction was only 40%. But the yield of RMA obtained by the reaction in carbon tetrachloride solution was 48%(theoretical yield 87.6%) and that obtained by the reaction in acetic acid solution was 51.5%(theoretical yield 94%) respectively.

• Bulletin of the Korean Chemical Society
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• v.20 no.4
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• pp.422-426
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• 1999

The Grignard reactions of bis(chloromethyl)dimethylsilane (1) with trimethylchlorosilane (2) in THF give both the intermolecular C-Si coupling and intramolecular C-C coupling products. At beginning stage, 1 reacts with Mg to give the mono-Grignard reagent ClCH2Me2SiCH2MgCl (1) which undergoes the C-Si coupling reaction to give MC2Si(CH2SiMe3)2 3, or C-C coupling to a mixture of formula Me3SiCH2(SiMe2CH2CH2)nR1 (n = 1, 2, 3, ..; 4a, R1I = H: 4b, R1 = SiMe3). In the reaction, two reaction pathways are involved: a) Ⅰ reacts with 2 to give Me3SiCH2SiMe2CH2Cl 6 which further reacts with Mg to afford a Me2SiCH2Mel-SiCH2MgCl (Ⅱ) or b) I cyclizes intramolecularly to a silacyclopropane intermediate A, which undergoes a ring-opening polymerization by the nucleophilic attack of the intermediates I or Ⅱ, followed by the termination reaction with H2O and 2, to give 4a and 4b, respectively. As the mole ratio of 2/1 increased from 2 to 16 folds, the formation of product 3 increased from 16% to 47% while the formation of polymeric products 4 was reduced from 60% to 40%. The intermolecular C-Si coupling reaction of the pathway a becomes more favorable than the intramolecular C-C coupling reaction of the pathways b at the higher mole ratio of 2/1.

• Macromolecular Research
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• v.17 no.5
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• pp.339-345
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• 2009

The core/shell type structure of the highly crosslinked poly(glycidylmetharylate-co-divinylbenzene) microspheres prepared in the precipitation polymerization in acetonitrile was thoroughly verified by means of swelling, $^1H$ NMR, XPS, TEM and TGA measurements. In the XPS measurement, the higher the GMA content, the higher the oxygen content was observed, implying that the higher content of GMA is observed in the particle surface. The further verification of the core/shell structure of the poly(GMA-co-DVB) particles was carried out using $^1H$ NMR and TEM techniques, resulting in the poly(GMA-co-DVB) particles with the GMA rich-phase and DVB rich-phase. In overall, the poly(GMA-co-DVB) microspheres consist of a highly crosslinked DVB rich-phase in the core and slightly or non-crosslinked GMA rich-phase in the shell part due to the different reaction ratios between two monomers and self-crosslinking density of DVB.

• Proceedings of the Korean Fiber Society Conference
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• 2003.10a
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• pp.91-91
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• 2003

Major factors including solvent and reaction temperature in the cationic polymerization of isobutyl vinyl ether (IBVE), photoinduced in the presence of diphenyliodonium iodide (DPII) zinc iodide in toluene/diethyl ether mixed solvent has been investigated. It was found that the living nature of the propagating species and the tacticity of the resulting polymer is significantly dependent on these factors. The addition of diethyl ether (DEE) results in not only the loss of the cationic living nature but also decrease in the isotactic content.

• 한국생물공학회:학술대회논문집
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• 2003.04a
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• pp.121-125
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• 2003

Enzymatic polymerization of cardol derived from cashew nut shell liquid have been examined. t-Butyl alcohol aqueous systems showed high yield of polycardol when SBP was as biocatalyst. Compared other solvents, peroxidase actiyity was maintained stable, which was seemed major cause. Solvent aqueous system and concentration of hydrogen peroxide were found to have an influence on the yield and molecular weight distribution of polycardol under the reaction of enzymatic polymerization using peroxidase. The polymer was subjected to the hardening by methyl ethyl ketone peroxide and cobalt naphthenate catalyst, giving a crosslinked tough film. Polycardol was cured rapidly and the hardness increased with time. Finally, the pencil scratch hardness reached to 7H, which is enough hard for industrial uses.