• Macromolecular Research
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• 제14권4호
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• pp.466-472
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• 2006

The kinetic behavior of emulsion polymerizations of styrene in the presence of sulfonated N-hydroxy ethyl aniline (SHEA) was investigated with two initiators: 2,2'-azobisisobutyronitrile (AIBN) and potassium persulfate (KPS). SHEA was synthesized using a stepwise polyurethane reaction method from 3-hydroxy-1-propane sulfonic acid sodium salt, isophorone diisocyanate (IPDI), and N-(2-hydroxyethyl) aniline. Stable core-shell poly(styrene/sulfonated N-hydroxy ethyl aniline, St/SHEA) latex particles were successfully prepared by using an appropriate amount of AIBN, in which SHEA plays the role of 'surfmer', i.e., acting as both a surfactant in the emulsion polymerization and a monomer in the chemical oxidative polymerization. The kinetic behavior was dissimilar to that of typical emulsion polymerization systems. A long inhibition period and low rate of polymerization were observed due to radical loss by the oxidative polymerization of SHEA. It was concluded, due to the low water-solubility of AIBN and retardation reaction by SHEA, that the initial loci of polymerization were monomer droplets. However, growing polymer particles as polymerization loci became predominant as polymerization proceeded. It was suggested that AIBN was more effective than KPS in the preparation of the core-shell type poly(St/SHEA) latex particles. With KPS, no substantial polymerization was observed in any of the samples.

• Fibers and Polymers
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• 제5권1호
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• pp.75-81
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• 2004

To obtain high molecular weight (HMW) poly(methyl methacrylate) (PMMA) with high conversion, methyl methacrylate (MMA) was polymerized in suspension using a room temperature initiator, 2,2'-azobis(2,4-dimethylvaleronitrile) (ADMVN), and the effects of polymerization conditions on the polymerization behavior of MMA and the molecular parameters of PMMA were investigated. On the whole, the experimental results well corresponded to the theoretically predicted tendencies. These effects could be explained by a kinetic order of ADMVN concentration calculated by an initial rate method and an activation energy difference of polymerization obtained from the Arrhenius plot. Suspension polymerization at 25℃ by adopting ADMVN proved to be successful in obtaining PMMA of HMW (number-average degree of polymerization (P/sub n/): 30,900-36,100) and of high yield (ultimate conversion of MMA into PMMA: 83-93 %) with diminishing heat generated during polymerization. The P/sub n/ and lightness were higher and polydispersity index was lower with PMMA polymerized at lower temperatures.

• Macromolecular Research
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• 제11권3호
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• pp.146-151
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• 2003

The dependence of electrical conductivity on concentrations of diallyldimethylammonium chloride (DADMAC) monomer, linear poly(DADMAC) and their mixture monomer/poly(DADMAC) in dilute aqueous solution exhibits a linear relationship. It was possible to calculate conversion of DADMAC polymerization by measuring its electric conductivity. Although the electrical conductivity of the poly(DADMAC) solution decreased with increasing its molecular weight, in the process of UV or ionizing radiation polymerization the molecular weight of the polymers could be kept constant in the case of fixed temperature, UV-luminous intensity or dose rate. Based on the method mentioned above, the kinetics of UV induced polymerization of DADMAC in aqueous solution was studied; the overall activation energy of polymerization of DADMAC in the water phase was calculated to be 18.8 kJ mol$^{-1}$ . ${\gamma}$-Radiation-induced polymerization of DADMAC in aqueous solution as a function of absorbed dose was studied as well. The conversion of DADMAC increased quickly with dose before 30 kGy and then increased slowly. The experimental data of both UV- and ${\gamma}$-induced polymerization were verified to be reliable by inverted ultracentrifugation method.

• 폴리머
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• 제24권5호
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• pp.610-620
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• 2000

아세트산비닐(VAc)을 아조비스디메틸발레로니트릴(ADMVN) 및 삼차부틸알코올 (TBA)을 각각 개시제 및 용매로 하여 30, 40 및 5$0^{\circ}C$에서 용액중합하였다. 합성된 폴리아세트산비닐 (PVAc)을 비누화함으로써 고분자량 혼성배열 폴리비닐알코올(PVA)을 제조하였다. 중합조건들이 전환률, 가지화도 및 PVAc와 PVA의 분자량에 미치는 영향을 고찰하였다. TBA에서의 VAc의 중합 속도는 ADMVN 농도의 0.49승에 비례하였고, 이는 이론치 0.5와 잘 일치하였다. 저온에서 개시가 가능한 ADMVN 및 낮은 사슬이동상수를 갖는 TBA를 사용함으로써 고분자량 및 고수율의 PVA가 얻어졌다. PVAc의 평균 중합도는 전환률 약 35%부터 70%의 범위에서 10000~13000이었고, 이를 비누화하여 얻은 PVA의 평균 중합도는 2400~6100이었다. 교대배열 다이애드기 함량은 중합온도를 낮춤에 따라 조금씩 증가하였고, 중합시 TBA의 입체장애 효과 때문에 TBA의 양을 증가시킴에 따라서도 증가하였다.

• 접착 및 계면
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• 제2권2호
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• pp.11-19
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• 2001

트리카프릴메틸 암모니움 클로라이드를 상이동촉매로 사용하여 $Na_2S_2O_8$의 수용액과 톨루엔의 이상계에서 질소분위기하에 $60^{\circ}C$에서 스티렌의 라디칼중합을 행하였다. 중합시의 초기 중합속도는 촉매와 $Na_2S_2O_8$의 초기공급 농도보다는 수용액 상에서의 4급 암모늄양이온과 퍼록시디슬페이트 음이온의 농도로 나타낼 수 있었다. 관찰된 초기중합속도를 사용하여 분균일 액-액계에서의 순환 상이동에 의한 개시과정을 포함한 중함메카니즘을 밝힐 수 있었다. 폴리스티렌의 점도평균분자량은 $Na_2S_2O_8$의 농도에 역비례하였는데, 라디칼 중합메카니즘에 의하여 $[Q^+]([S_2O{_8}^{2-}]{\alpha}_2)^{1/2}$로 나타내어졌다.

• 대한전기학회논문지
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• 제43권5호
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• pp.802-808
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• 1994

The purpose of this paper is to describe an application of plasma polymerized thin film as an electron beam resist. Plasma polymerized thin film was prepared using an interelectrode capacitively coupled gas-flow-type reactor, and chosen methylmethacrylate(MMA)and methylmethacrylate-tetrameth-yltin(MMA-TMT) as a monomer. This thin films were also delineated by the electron-beam apparatus with an acceleration voltage of 30kV and an expose dose ranging from 20 to 900$\mu$C/cmS02T. The delineated pattern in the resist was developed with the same reactor which is used for polymerization using an argon as etching gas. The growth rate and etching rate of the thin film is increased with increasing of discharge power. Thin films by plasma polymerization show polymerization rate of 30~45($\pm$3) A/min, and etching rate of 440($\pm$30) A/min during Ar plasma etching at discharge power of 100W. In apparently lower than that of conventional PMMA, but the plasma-etching rate of PP(MMA-TMT) was higher than that of PPMMA.

• Restorative Dentistry and Endodontics
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• 제33권4호
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• pp.341-351
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• 2008

지금까지 다수의 연구자들에 의해 광중합형 복합 레진을 중합하는 방법에 있어서 광조사 강도, 시간을 조절하여 중합수축의 속도를 감소시키기 위한 시도가 있었으나, 간헐적 중합법에 관한 구체적인 연구가 부족하다. 이에 저자는 광중합 복합 레진을 간헐적으로 광중합시켜 기존의 연속 중합법과 비교하여 중합 수축의 속도를 측정하고 교두 변위에 대한 영향을 평가해 보고자 하였다. 실험에 사용된 수복 재료는 2종의 광중합형 복합 레진으로 Heliomolar와 Pyramid이며, 중합 수축량을 측정하기 위해 자체 제작한 Linometer (R&B Inc., Daejon, Korea)을 사용하였고 광중합시 광조사 차단장치를 시편과 Linometer 사이에 위치시켜 각각의 서로 다른 중합 주기: (1) 연속 광중합 (60초간 계속 광조사); (2) 2초 광조사, 1초 광차단 (90초 시행), (3) 1초 광조사, 1초 광차단 (120초 시행), (4) 1초 광조사, 2초 광차단 (180초 시행)로 중합시켰다. 군 별로 조사된 총에너지량이 동일하도록 중합 시간을 조절하였고, 최종 중합 수축량을 측정하였으며 중합 수축의 최고속도 ($R_{max}$)와 최고속도를 나타낸 peak time (PT)을 계산하였다. 교두 변위의 측정을 위해서는 각 군별로 10개의 건전한 상악 소구치에 변형시킨 제2급 와동을 형성한 다음 상아질 접착제를 도포하고 일정량의 복합 레진을 충전한 후 치아를 자체 제작된 치아 변위 측정기 (R&B Inc., Daejon, Korea)에 위치시켜 교두 변위양을 알아보았다. 통계분석은 ANOVA test를 이용하여 군 간의 비교를 하였고, 재료간의 비교를 위해서는 t-test를 시행하였다. 실험 결과는 1) 선수축량은 군 간에 차이가 없었고 (p > 0.05), Pyramid가 Heliomolar보다 중합 수축량이 컸다 (p < 0.05). Peak time은 Heliomolar와 Pyramid 레진 모두에서 간헐적 광중합시 더 늦게 나타났다. $R_{max}$는 Heliomolar는 4군 < 3군, 2군 < 1군 순이었고, Pyramid는 3군 < 4군 < 2군, 1군 순으로 측정되었다. 2) Heliomolar는 4군 < 3군 < 2, 1군 그리고 Pyramid는 4, 3군 < 2, 1군 순으로 교두 변위가 컸으며 (p < 0.05), Pyramid가 Heliomolar보다 교두 변위가 크게 나타났다 (p < 0.05). 이번 실험을 통해 복합 레진을 광조사 차단장치를 이용하여 간헐적 광중합시켜 중합수축 속도를 늦춤으로써 교두 변위 양이 감소됨을 알 수 있었다.

• 한국섬유공학회:학술대회논문집
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• 한국섬유공학회 2003년도 The Korea-Japan Joint Symposium
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• pp.1-2
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• 2003

Some new synthetic routes for the preparation of poly (isobutyl vinyl ether) (P(IBVE)) having a controllable molar mass with narrow distribution via catalytic or photoinduced living cationic polymerization and their conversion to corresponding PVA have been developed. It was found that the combination of iodomethyl methyl ether (IMME)-zinc iodide is effective in the initiation of the catalytic and the various combinations of diphenyliodonium halides, well known photocationic initiators (DPIX) with zinc halides (ZnX$_2$) are also useful in photoinduced living cationic polymerization of isobutyl vinyl ether (IBVE). Polymerization both in the catalytic and photoinduced systems precede until the full consumption of the monomer and the rate of polymerization increases as the concentration of the catalyst or photoinitiator. The number average molar mass of the resulting polymer is proportional with % conversion, which is determined by the ratio of monomer consumed and the initial values of the catalyst or initiator. The living nature was also confirmed by subsequent monomer addition technique.

• 공업화학
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• 제2권3호
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• pp.199-208
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• 1991

양이온 중합은 electron이 풍부한 단량체들을 중합하는데 널리 이용되나 많은 부 반응과 빠른 중합속도 때문에 반응을 제어하기가 어렵다. 최근에 이러한 반응 제어에 많은 연구가 되고 있는데 특히 living 중합에 의하여 중합반응을 제어하는 방법에 대한 연구가 활발하다. 본고에서는 종합활성점의 해리상태를 조절하여 중합반응을 제어하고 living 중합을 도모하는 방법에 대하여 기술하였다. 그리고 현재까지 알려진 여러 방법들을 이러한 기본원리하에서 설명하였다.

• Fibers and Polymers
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• 제2권1호
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• pp.131-134
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• 2001

Living cationic polymerization behaviors of isobutyl vinyl ehters (IBVE), initiated by iodomethyl methyl ether (IMME)/zinc iodide ($Znl_2$) have been investigated. The polymerization was carried out at 0, -15, and $-30^{\circ}C$ in toluene. It was found that the rate of polymerization increased as the IMME concentration increased and decreased as temperature decreased. 100% conversion was always achieved without exception. Furthermore, the number-average molecular weight ($M_{n}$) of polymers increased in direct proportion to monomer conversion. The molecular weights of polymers were in good agreement with the theoretical values, calculated on the basis that one polymer chain was formed by one IMME molecule and the values of polydispersity index are always less than 1.2, revealing the living nature. The living nature was also confirmed by synthesis of poly(IBVE-b-TBVE) by subsequent monomer addition of t-butyl vinyl ether (TBVE).