• Macromolecular Research
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• 제10권6호
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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.

• 한국염색가공학회지
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• 제7권4호
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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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• 제24권2호
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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 $440^{\circ}C$.

• 폴리머
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• 제35권1호
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• pp.66-71
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• 2011

현탁중합에 이은 프리델 크래프츠 촉매에 의한 hyper crosslinking 반응 및 hydrolysis반응으로 hydroxyl 반응 관능기를 포함하는 hyper crosslinked polymer particle(HCPP)을 합성할 시, 1) 각 단량체의 함량 변화에 따른 HCPP의 표면 모폴로지, 기공 크기 및 분포도의 변화, 2) hyper crosslinking 반응조건 변화에 따른 HCPP의 BET 비표면적 값의 변화 및 3) $CO_2$ 초임계 건조공정을 이용한 HCPP에서의 미반응 잔류 단량체, 올리고머 및 촉매의 제거 등에 관해 연구하였다. 이번 연구를 통해 초기 HCPP의 합성 시 관찰되었던 고분자 입자 표면의 균열 및 파괴현상은 hyper crosslinking 과정 중에 진행되는 microphase separated domain간의 반응과 깊은 관계가 있음을 관찰하였고, 또한 hyper crosslinking 반응 시 반응온도 반응시간 및 사용 용매의 증가는 HCPP의 BET 비표면적 값의 증가에 기여함을 관찰하였다. 그리고 hyper crosslinking을 유발하는 단량체의 함량변화는 다른 단량체에 비해 HCPP의 BET 비표면적, 기공 크기 및 분포도에 상대적으로 큰 영향을 미침을 확인하였다. 또한 HCPP에서의 미반응 잔류 단량체, 올리고머 등의 제거에 $CO_2$ 초임계 건조공정이 매우 효과적임을 확인할 수 있었고 특히 이 과정에서의 보조용매(메탄올)의 첨가는 잔류촉매(Fe)의 제거에 있어 탁월한 효과를 나타내었다.

• 한국추진공학회지
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• 제18권5호
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• pp.35-42
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• 2014

본 연구에서는 시차주사열량계시험, 반응열시험, 접착전단시험을 통해 자가치료제의 열분석 특성과 접착 특성을 평가하였다. 자가치료제는 DCPD와 ENB의 혼합비에 따라 D1E0, D3E1, D1E1, D1E3, D0E1을 고려하였다. 촉매는 Grubbs' catalyst를 자가치료제의 종류에 따라 0.1 wt%에서 1.5 wt%까지 적용하였다. DCPD의 경우는 촉매 양이 많을수록 중합반응이 빠르고 안정화된 접착강도가 높아지지만 많은 양의 촉매가 요구된다. ENB의 경우 촉매와의 반응성이 우수하여 적은 양의 촉매로도 빠른 중합반응을 얻을 수 있지만 반응열이 높게 나타난다. DCPD와 ENB의 혼합비를 변화시키면 자가치료제의 열분석 특성 및 접착 특성을 조절할 수 있으며 본 연구에서 고려한 자가치료제 중 D3E1가 최대접착강도, 최대접착강도에 도달하는 시간, 안정화된 접착강도, 반응열 측면에서 자가치료제로 가장 유리함을 알 수 있다.

• 공업화학
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• 제5권2호
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• pp.313-320
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• 1994

로진과 말레산무수물로부터 rosin-maleic anhydride adduct(RMA)를 합성하였다. 중합반응의 단량체로서 이용하기 위한 고순도의 RMA의 합성에는 정제공정을 수반하는 용융합성법과 정제공정이 불필요한 용액합성법을 이용하였다. 용액합성법에서 합성한 RMA의 수율이 용융합성업보다 높았다. 용융합성법의 최고수율은 40%였으나 사염화탄소 및 아세트산을 반응용제로하는 용액합성법에서 얻은 생성물의 수율과 순도를 검토한 결과 비교적 고순도의 RMA를 얻을 수 있었고, 수율은 사염화탄소 용제법의 경우 48%(이론수율 87.6%), 아세트산 용제법의 경우 51%(이론수율 94%)였다.

• Bulletin of the Korean Chemical Society
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• 제20권4호
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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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• 제17권5호
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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.

• 한국섬유공학회:학술대회논문집
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• 한국섬유공학회 2003년도 The Korea-Japan Joint Symposium
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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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• 한국생물공학회 2003년도 생물공학의 동향(XII)
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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.