• Title/Summary/Keyword: 중합반응속도

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Dithioester 와 xanthate agent 가 매개된 RAFT 중합반응에서 Z 치환기의 변화로 인한 안정성 효과에 대한 연구

  • Baek, U-Hyeon;Sin, Chae-Su;Sin, Seok-Min
    • Proceeding of EDISON Challenge
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    • 2016.03a
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    • pp.23-31
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    • 2016
  • 자유 라디칼을 이용한 RAFT 중합은 성장하는 고분자 반응을 제어할 수 있는 특성이 있어 주목 받고 있는 고분자 합성방법 중 하나이다. 이 반응의 기작은 agent라 불리는 분자를 주축으로 삼아 단량체들을 단계적으로 성장하는 가역적 방법으로 원하지 않는 종결반응으로부터 고분자 라디칼을 보호하는 역할을 수행한다. 보호의 근본적인 원인은 중간체 상태에서의 안정화 정도와 관련이 있으나 안정해진 만큼 반응속도가 느려지는 지연효과가 발생한다. 지연효과를 유도하는 원인은 많은 논란이 있었으며 그 중 하나로 agent에 존재하는 Z 치환기의 영향을 원인으로 지목하고 있다. 본 연구는 Z 치환기의 변화에 따른 안정화 정도를 파악하기 위하여 RAFT agent로 주로 이용하는 것 중 두 개의 황이 있는 dithioester와 xanthate를 WxMacMolplt 7.3.2를 이용하여 propagation 초기 단계를 구현한 후 GAMESS2 프로그램을 이용하여 양자화학적 계산을 수행하였다. 계산결과 안정화 에너지와 경계 궤도함수에서는 phenyl기가 있을 때 공명효과에 의하여 안정화가 이루어졌으며 또한 propyl benzyl에서도 늘어난 알킬 사슬의 donating effect로 인한 안정화 영향의 범위를 발견하였다. PES 기법을 통해 두 methyl 단량체를 움직이면서 반응하는 동안의 에너지 변화를 알아보았으며 그 결과 dithioester는 Z 치환기의 변화에 더 많이 의존한다는 것을 확인하였다. 본 연구를 종합해본 결과 phenyl을 제외한 aryl기가 있는 dithioester는 낮은 addition 퍼텐셜과 안정화 에너지를 가질 수 있을 것이고 지연효과를 줄일 수 있을 것으로 기대된다.

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Preparation of Micron Size Poly(n-Butyl Acrylate) Latex Particle by Sequential Seeded Emulsion Polymerization (연속적 Seed 유화중합법에 의한 마이크론 크기의 Poly(n-Butyl Acrylate) 라텍스입자 제조)

  • Kim, Jee-Hoon;Suh, Soong-Hyuck;Nam, Wan-Woo;Kim, Kyung-Chan;Kang, Shin-Won;Ha, KiRyong
    • Applied Chemistry for Engineering
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    • v.10 no.6
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    • pp.889-894
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    • 1999
  • Preparation of micron size polymer particles which have desired morphology, size, and structure by emulsion polymerization is very difficult due to coagulation of latex particles and formation of second generation particles. But there are attractive merits such as preparation of structural and functional polymer particles in seeded emulsion polymerization. Seeded emulsion polymerization of n-butyl acrylate(BA) was carried out to investigate the effects of stirring rate, reaction temperature, concentration of initiator, emulsifier, and cross-linking agent on the particle size and size distribution. By the combination of suitable reaction conditions, we succeeded in preparing $0.14{\sim}3.67{\mu}m$ diameter of poly(n-butyl acrylate)(PBA) particles using sequential seeded emulsion polymerization.

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Measurement of Viscosity Behavior in In-situ Anionic Polymerization of ε-caprolactam for Thermoplastic Reactive Resin Transfer Molding (반응액상성형에서 ε-카프로락탐의 음이온 중합에 따른 점도 거동 평가)

  • Lee, Jae Hyo;Kang, Seung In;Kim, Sang Woo;Yi, Jin Woo;Seong, Dong Gi
    • Composites Research
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    • v.33 no.2
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    • pp.39-43
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    • 2020
  • Recently, fabrication process of thermoplastic polyamide-based composites with recyclability as well as impact, chemical, and abrasion resistance have been widely studied. In particular, thermoplastic reactive resin transfer molding (TRTM) in which monomer with low viscosity is injected and in-situ polymerized inside mold has received a great attention, because thermoplastic melts are hard to impregnate fiber preform due to their very high viscosity. However, it is difficult to optimize the processing conditions because of high reactivity and sensitivity to external environments of the used monomer, ε-caprolactam. In this study, viscosity as an important process parameter in TRTM was measured during in-situ anionic polymerization of ε-caprolactam and the solutions for problems caused by high polymerization rate and sensitivity to moisture and oxygen were suggested. Reliability of the improved measurement technique was verified by comparing the viscosity behavior at various environmental conditions including humidity and atmosphere, and it is expected to be helpful for optimization of TRTM process.

Mesoporous Silica Catalysts Modified with Sulfonic Acid and Their Catalytic Activity on Ring Opening Polymerization of Octamethylcyclotetrasiloxane (술폰산으로 표면개질된 메조기공 실리카 촉매의 제조 및 Octamethylcyclotetrasiloxane 개환중합에서의 촉매 활성)

  • Lee, Yeonsong;Hwang, Ha Soo;Lee, Jiyoung;Lo, Nu Hoang Tien;Nguyen, Tien Giang;Lee, Donghyun;Park, In
    • Applied Chemistry for Engineering
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    • v.31 no.4
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    • pp.383-389
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    • 2020
  • Mesoporous silica solid catalysts modified with sulfonic acid were prepared for cationic ring-opening polymerization of octamethylcyclotetrasiloxane (D4). Two sets of MCM-41 (1.7 and 2.8 nm) and SBA-15 (8.1 and 15.9 nm) with different pore sizes were used as catalyst supports. The surface of silica materials was modified with (3-mercaptopropyl)trimethoxysilane by silylation reaction and oxidized to sulfonic acid. The structures of the prepared catalysts were examined by X-ray diffraction and nitrogen adsorption-desorption. The pore size, specific surface area, and pore volume of the modified solid catalysts decreased slightly. In addition, the modification of the sulfonic acid on the silica surface was confirmed by using infrared spectroscopy and nuclear magnetic resonance spectroscopy. To observe the effect of the particle size on the catalytic activity, it was observed with a scanning electron microscope. The catalysts were used to synthesize PDMS through a ring-opening polymerization of D4, and the conversion and polymerization rate of the polymerization reaction depended on the pore size, specific surface area, particle size, and particle agglomeration of the catalysts. In order for the polymerization rate, the catalyst prepared with SBA-15 of 8.1 nm pore size had the fastest reaction rate and showed the best catalytic activity.

Radiation Induced-Grafting of Acrylic Acid onto Polyvinyl Chloride Fibers

  • Park, Jae-Ho;Lee, Chong-Kwang
    • Nuclear Engineering and Technology
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    • v.8 no.2
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    • pp.89-99
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    • 1976
  • The grafting of acrylic acid in aqueous solution to polyvinyl chloride fibers tab been studied in the presence of ferrous, ferric, and cupric salts, The mutual irradiation technique was adopted using a Co-60 source or a Van do Graaff accelerator. The grafting and homopolymerization were suppressed by the cations. Particularly the grafting was suppressed by the cations in the following order of effectiveness : $Cu^{2+}$>$Fe^{2+}$>$Cu^{3+}$. The rate of grafting (in %/hr) was proportional to the 0.76th power of the dose rate over the range from 8.5f $10^3$ rad/hr to $1.4\times10^5$ rad/dr. The apparent activation energy for the grafting was determined to be 6.1 Kcal/mole between $25^{\circ}$ and $75^{\circ}C$ for the mixture of AA-HaO-$(CH_2Cl)_2$, containing Mohr's salt, $4\times10^{-3}$ mole/l. The increase of the grafting was observed when total dose and dose intensity were raised, or when ethylene dichloride as a swelling agent was saturated in the monomer mixture. The grafted polyvinyl chloride fibers showed considerable improvement in moisture regain, heat shrinkage, and melting properties, but tensile properties were not significantly affected by grafting.

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Preparation of Poly(butyl methacrylate) Composite Beads containing Carbon Black by Suspension Polymerization (현탁중합법에 의한 카본블랙을 함유하는 폴리뷰틸메타크릴레이트 복합체 입자의 합성)

  • Moon, Ji-Yeon;Park, Moon-Soo
    • Elastomers and Composites
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    • v.43 no.3
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    • pp.157-165
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    • 2008
  • Suspension polymerization was carried out to synthesize poly(butyl methacrylate) (PBMA) composite particles containing carbon black. Water was selected as a reaction medium, hydrophobic silica as a stabilizer and azobisisobutyronitrile as an initiator. Concentration of stabilizer was varied from 0.67 to 2.55 weight% with respect to the water, and that of initiator was varied from 0.25 to 3.00 weight% with respect to the butyl methacrylate (BMA) monomer. All polymerization reactions were conducted at 75$^{\circ}C$. It is found that stabilizer concentration has no impact on reaction kinetics, while an increase in initiator concentration enhances polymerization reaction rate. Increase of carbon black concentration from 1 to 3 to 5 wt% into PBMA displayed progressive decrease in reaction conversion. The particle diameter of PBMA composite particles containing carbon black was found to be between 5 and 30 ${\mu}m$. Glass transition was determined to range from 23.8 to 24.7$^{\circ}C$, irrespective of variation in the concentration of stabilizer, initiator or carbon black.

Manufacture of Core-Shell Composite Polymer Materials for Nonwoven binder (부직포 바인더용 Core-Shell 복합소재의 제조)

  • Lee, Sun Ryong;Lim, Jae Keel;Seul, Soo Duk
    • Journal of Adhesion and Interface
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    • v.3 no.4
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    • pp.27-36
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    • 2002
  • The organic/organic core-shell composite polymer for nonwomen binder were synthesized by stage polymerization of methyl methacrylate and styrene with ammonium persulfate after preparing monomer pre-emulsion in the presence of anionic surfactant. We study the effect of initiator concentration, $0.79{\times}10^{-3}{\sim}3.16{\times}10^{-3}mol/L$ for core polymer, $2.0{\times}10^{-4}{\sim}8.0{\times}10^{-4}mol/L$ for shell polymer, sulfactant concentration, $1.45{\times}10^{-5}{\sim}4.15{\times}10^{-5}mol/L$ for core polymer, $0.73{\times}10^{-5}{\sim}2.91{\times}10^{-5}mol/L$ for shell polymer on core-shell structure of polymethyl methacrylate/polystyrene and polystyrene/polymethyl methacrylate. Emulsion stability was major test method, particle size and particle size distribution were measured using particle size analyzer and the morphology of the core-shell composite polymer was determined using transmission electron microscope, glass temperature was also measured using differential scanning calorimeter.

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Photodegradation of Cellulosics(Part II) - Chemical Properties of Irradiated Cotton - (Cellulose의 광분해에 관한 연구(II) - 광조사된 면섬유의 화학적 성질을 중심으로 -)

  • 전경숙
    • Journal of the Korean Society of Clothing and Textiles
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    • v.18 no.1
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    • pp.15-22
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    • 1994
  • The formation of carbonyl group was dominant to other functional groups. Concentrations of both carboxyl and peroxide groups were found to rapidly reach low steady state values that increased slightly with increa-sing temperature and relatice humidity. Since the deg-radation of cellulose samples was in the initial stage and the conversion of glycosidic bonds and hydroxyl groups were very small, it was found that changes in the physical and chemical properties could be fitted to a first-order reaction model.

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Photodegradation of Cellulosics -Part 1: Effects of Temperature and Humidity on Tear Strength Reduction- (면섬유의 Photodegradation에 대한 연구 -온도, 습도가 인열강도 감소에 미치는 영향-)

  • Jeon Kyung Sook
    • Journal of the Korean Society of Clothing and Textiles
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    • v.16 no.2
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    • pp.181-187
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    • 1992
  • 일반적으로 면섬유는 햇빛에 의해서 변색되거나 약해지며 또 그 외에도 여러가지 물리적, 화학적인 변화를 일으키게 된다. 구체적인 화학반응의 메카니즘은 사용되는 광선의 스펙트럼, 대기조건(실내인 경우는 실내 환경조건) , 산소의 유무 그리고 염료 등 첨가물의 종류와 같은 여러 요소에 의해 크게 영향을 받게 된다. 환경조건 중에서 산소의 존재는 매우 중요하지만 open system에서 산소의 농도가 일정하다고 가정할 때 면섬유가 접하고 있는 환경조건 중에서 온도와 습도는 photodegradation의 속도를 결정짓는 중요한 요인으로 작용하게 된다. 박물관,:기념관, 도서관 등의 소장품이 자연광선이나 인공조명으로부터 손상되는 것을 막기 위해서는 먼저 이들의 photodegradation 현상에 대한 연구를 필요로 한다. 본 연구에서는 면시칩포를 자연광선과 가장 흡사한 스펙트럼을 가진 xenon arc lamp를 사용한 내후도 시험기내에서 온도와 습도를 조절하여 이에 따른 반응속도의 차이를 인열강도의 감소와 중합도 저하로 측정하였다. 1차 반응식은 실험결과를 설명하는데 유용하였으며 온 · 습도의 증가는 반응속도를 증가시키는 것으로 나타나 기존의 상반된 연구결과의 차이를 입증하였다. 또 온도와 습도는 상호관련이 있는 것으로 나타났으며 고온인 경우습도의 영향을 더 크게 받는 것으로 분석되었다. 반응의 활성에너지는 $30\~75\%$ RH에서는 12 kcal/mole 정도이며 수분의 함량이 낮을수록 활성화에너지는 커지는 것으로 나타나 수분은 섬유소 분자구조내에서 가소제 (plasticizer)의 역할을 하는 것으로 판명되었다.

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Rapid Detection of Enterotoxigenic Staphylococcus aureus by Polymerase Chain Reaction (중합효소 연쇄반응에 의한 식중독성 황색포도상구균의 신속한 검출)

  • Kim, Eun-Seon;Jhon, Deok-Young
    • Korean Journal of Food Science and Technology
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    • v.28 no.6
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    • pp.1001-1008
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    • 1996
  • Staphylococcal food poisoning is the major cause of bacterial food poisoning occurring in this country. Therefore government regulates commercial foods through Official Dictionary of Food that there should be free of enterotoxigenic Staphylococcus aureus in Korean rice cakes, bread, and a box lunch. Since at least 5 days are required to identify the S. aureus by the official method in the Dictionary it is difficult to prevent the food poisoning and the investigation of the outbreaks. In this report an improved determination method of the S. aureus has been developed using polymerase chain reaction (PCR) technique. Sense and antisense primers for specific amplification of genes encoding staphylococcal enterotoxins were designed and synthesized for the PCR. Rapid chromosomal DNA isolation method was also developed from S. aureus using lysostaphin. The PCR condition was developed as follows. Reaction solution $(50\;{\mu}l)$ consisted of target DNA $2\;{\mu}l$ (about 20ng), 10X buffer $5\;{\mu}l$, primer 100pmole, dNTP (10 mM) $4\;{\mu}l$ and Taq DNA polymerase 2.5 unit in a thin-wall tube. Operation condition of the PCR was 5 min pre-denaturation at $94^{\circ}C$, 15 sec denaturation at $94^{\circ}C$, 15 sec annealing at $50^{\circ}C$, 20 sec extension at $72^{\circ}C$, and 5 min post-extension at $72^{\circ}C$, and 30 cycles of denaturation-annealing- extension. Using the PCR with Perkin Elmer GeneAmp PCR system 2400, types of enterotoxigenic S. aureus could be identified from Ddok or bread in a day.

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