• 제목/요약/키워드: polymerization rate

검색결과 360건 처리시간 0.029초

실시간 In-situ IR을 이용한 Glycidyl Azide Monomer(GAM)의 양이온중합 반응속도 연구 (Kinetic Study on the Cationic Polymerization of Glycidyl Azide Monomer(GAM) by Real-Time In-suti IR)

  • 김형석;김관영;강신춘;노시태;김진석;유재철;최근배
    • 한국군사과학기술학회지
    • /
    • 제12권2호
    • /
    • pp.228-235
    • /
    • 2009
  • We synthesized glycidyl azide monomer(GAM) as a monomer for polymerization of glycidy azide polymer(GAP) which is a promising energetic prepolymer for a plastic-bonded explosive. Using quantitative real-tim in-situ infrared(in-situ IR) spectroscopy, kinetic study on the cationic ring opening polymerization of GAM was carried out. The reaction rate was obtained from monitoring the change of ether C-O stretching band($1050cm^{-1}$) in series IR spectra. The reaction was in accordance with the first-order reaction law for each of reaction temperature at 100/1 mole ratio of [GAM]/[$BF_3*etherate$]. In the ring opening polymerization of GAM, with ratio of [GAM]/[$BF_3*etherate$] to equal 100/1 at various temperature, the activation parameters obtained from the evaluation of kinetic data were ${\Delta}H^*$=14.34kcal/mol, ${\Delta}S^*=-12.31cal/mol{\cdot}K$ and $E_a$=14.89kcal/mol.

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

  • 문지연;박문수
    • Elastomers and Composites
    • /
    • 제43권3호
    • /
    • pp.157-165
    • /
    • 2008
  • 현탁중합법을 이용하여 카본블랙을 함유하는 폴리뷰틸메타크릴레이트 복합체 입자를 합성하였다. 물을 반응매체로 선택하고 소수성실리카를 안정제로 azobisisobutyronitrile (AIBN)을 개시제로 선택하였다. 안정제의 농도는 물에 대하여 0.67 중량%에서 2.55 중량%까지 변화시켰으며, 개시제는 단량체에 대하여 0.25 중량%에서 3.00 중량%까지 변화시키면서 반응역학에 미치는 영향을 조사하였다. 모든 반응은 75$^{\circ}C$에서 진행하였다. 안정제의 농도는 반응속도에 무관하였으나, 개시제의 증가는 반응속도를 증가시켰다. 카본블랙을 단량체에 대하여 1, 3 및 5 중량% 유입하는 경우 반응전환율은 단계적으로 감소하였다. 폴리뷰틸메타크릴레이트 복합체 입자의 입경은 5-30 ${\mu}m$로 관찰되었다. 유리전이온도는 카본블랙의 유입 및 개시제, 안정제의 농도에 무관하게 23.8-24.7$^{\circ}C$로 측정되었다.

가변 광도 중합에 따른 복합레진의 중합수축에 관한 연구 (POLYMERIZATION SHRINKAGE OF COMPOSITE RESINS CURED BY VARIABLE LIGHT INTENSITIES)

  • 임미영;조경모;홍찬의
    • Restorative Dentistry and Endodontics
    • /
    • 제32권1호
    • /
    • pp.28-36
    • /
    • 2007
  • 본 연구는 광중합형 복합레진 중합 시 기존의 중합법과 가변광도 중합형인 soft start 중합법 및 exponential 중합법 간의 중합수축효과를 비교하고자 하였다. 본 연구를 위해 3종의 복합레진 (Synergy Duo Shade, Z250, Filtek Supreme) 및 3종의 광조사기 (Spectrum 800, Elipar Highlight, Elipar Trilight)를 사용하였다. 총 중합시간은 40초로 일정하게 유지하였으며, 선형 중합수축률의 측정은 linometer를 이용하였으며, 90초간의 선형 수축률을 0.5초 간격으로 측정하였다. 재료별로 각 중합 방법별 시간에 따른 중합수축률을 one-way ANOVA test로 분석하여 최종 중합수축률에 도달하는 시간을 산출하였고, 90초 후 최종 선형 중합수축률을 two-way ANOVA test를 이용하여 재료, 광조사 방법, 재료 및 광조사 방법의 교호작용이 중합수축에 미치는 영향이 있는지를 검증하였다. 또한 90초까지의 선형 중합수축률에 대한 20초까지의 선형 중합수축률의 비를 two-way ANOVA로 비교하고, 각각의 통계치를 95% Scheffe test로 검증하였는바, 다음과 같은 결과를 얻었다 1. Supreme을 제외한 다른 군에서는 재료 및 광조사 방법에 관계없이 대부분의 중합 수축이 광조사 후 20초 이내에 이루어졌다 (p < 0.05). 2. 90초 후, 최종 중합수축률은 재료 (p = 0.000)와 광조사 방법 (p = 0.003) 모두 유의성 있는 영향을 끼쳤으나, 재료와 광조사 방법 상호간의 작용은 영향이 없었다. 3. 90초 후 최종 중합수축률은 총 광에너지가 가장 낮은 exponential 중합법에서 유의성 있게 낮았다 (p < 0.05). 4. 20초까지의 초기 수축률은 soft start와 exponential중합법 등 가변광도 중합이 conventional 중합법에 비하여 유의성 있게 낮은 수축률을 보였다 (p < 0.05). 본 실험 결과만을 토대로 볼 때, 가변광도 중합법은 초기 중합수축 속도를 감소시켜 수축응력을 감소시킨다고 볼 수 있다. 그러나 총 조사 광에너지의 차이로 인해 그 물리적 성질에 영향이 있을 수 있으므로 향후 이에 대한 더 많은 고찰이 필요할 것으로 사료된다.

Preparation of High Molecular Weight Atactic Poly(vinyl alcohol) by Photo-induced Bulk Polymerization of Vinyl Acetate

  • Lyoo, Won-Seok;Ha, Wan-Shik
    • Fibers and Polymers
    • /
    • 제2권2호
    • /
    • pp.108-115
    • /
    • 2001
  • Vinyl acetate was polymerized in ultraviolet-ray initiated bulk system at low temperatures using 2,2-azobis(2,4-dimethylvaleronitrile) (ADMVN) or 2,2-azobis(isobutyronitrile) (AIBN) as the photoinitiator, respectively. High molecular weight (HMW) poly(vinyl alcohol) (PVA) having number-average degree of polymerization ($P_n$) of 3,900-7,800 and syndiotactic diad (S-diad) content of 52.5-54.0% could be prepared by complete saponification of synthesized linear poly(vinyl acetate) (PVAc) having $P_n$ 5,900-9,400 obtained at conversion of below 30%. $P_n$ of PVA using ADMVN was larger than that of PVA using AIBN. On the other hand, conversion of the former was smaller than that of the latter, and it was found that the initiation rate of the ADMVN was lower than that of AIBN. This could be explained by a fact that the rate of photolysis of AIBN is faster than that of ADMVN due to the higher quantum yield or dissociation rate constant of AIBN than that of ADMVN. The $P_n$, syndiotacticity, and whiteness of PVA from PVAc polymerized at lower temperatures were superior to those of PVA from PVAc polymerized at higher temperatures.

  • PDF

Mastication에 의한 Polystyrene의 機械的分裂 (Mechanical Degradation of Polystyrene by Mastication)

  • 정기현;성좌경
    • 대한화학회지
    • /
    • 제17권4호
    • /
    • pp.298-305
    • /
    • 1973
  • Roll을 사용한 mastication에 의한 polystyrene(단독시와 rubber와의 blend시)의 기계적 분열에 대하여 검토한 결과는 다음과 같다. 1) Polystyrene 단독시의 기계적 분열속도는 Goto가 밝힌 중합도$(P_t-P_{\infty})$에 관하여 2차인 다음식에 적합함을 알았다. $-\frac{dP_t}{dt} = k_s(P_t-P_{\infty})^2$2 2)Polystyrene-rubber (SBR, BR) blend계에서 polystyrene성분의 분열은 단독시와 비스하게 일어났다. 3)본 실험 조건하에서 polystyrene-rubber (SBR, BR) blend계에서, polystyrene성분의 분열속도도 단독시와 같이 상기한 2차식에 근사적으로 적합됨을 알았다.

  • PDF

Controlling Size and Distribution for Nano-sized Polystyrene Spheres

  • Yun, Dong-Shin;Lee, Hyeong-Seok;Jang, Ho-Gyeom;Yoo, Jung-Whan
    • Bulletin of the Korean Chemical Society
    • /
    • 제31권5호
    • /
    • pp.1345-1348
    • /
    • 2010
  • Highly monodisperse polystyrene (PS) nanospheres were fabricated by surfactant-free emulsion polymerization in water using styrene, 2,2'-azobis(2-methyl propionamidine) dihydrochloride (AIBA), and poly(vinyl pyrrolidone) (PVP). The size and distribution of the PS nanospheres were systematically investigated in terms of initiator concentration, stabilizer concentration, reaction temperature, reaction time, and reactant concentration. With increasing AIBA initiator concentration, PS particle sizes are raised proportionally, and can be controlled from 120 to 380 nm. Particle sizes were reduced with increasing PVP concentration. This decrease occurs because a high PVP concentration leads to a large number of primary nuclei in the early stage of polymerization. When the reaction temperature increased, the sizes of the PS particles decrease slightly. The particles grew quickly during the initial reaction stage (1-3 h) and the growth rate became steady-state after 6 h. The PS sizes approximately doubled when the reactant (styrene, PVP, azo-initiator) concentrations were increased by a factor of eight.

Chain Transfer to Monomer and Polymer in the Radical Polymerization of Vinyl Neo-decanoate

  • Balic, Robert;Fellows, Christopher M.;Van Herk, Alex M.
    • Macromolecular Research
    • /
    • 제12권4호
    • /
    • pp.325-335
    • /
    • 2004
  • Molecular weight distributions of poly(vinyl neo-decanoate) produced by the bulk polymerization of the monomer to low conversions were investigated to obtain values of the rate constants for the chain transfer to monomer ( $C_{M}$). The value of $C_{M}$ of 7.5($\pm$0.6)${\times}$10$^{-4}$ was obtained from a logarithmic plot of the number distribution at 5,25, and 5$0^{\circ}C$, which suggests that the activation energy for chain transfer is on the order of 20-25 kJ ㏖$^{-1}$ . These plots were linear between the number and weight-average degrees of polymerization, but not over the whole molecular weight range for which a significant signal was observed in the gel permeation chromatography (GPC) trace. Modeling suggests that the deviations observed at high molecular weights can be explained by branching of the chains through chain transfer to the polymer, with a branching density as low as 10$^{-5}$ , without affecting the slope at low values of the number of monomer unit, N. This deviation from the expected distribution of linear chains was used to estimate the branching densities at low conversion.ion.

공정압력 및 기판바이어스 인가유무에 따른 PMMA 플라즈마중합박막의 전기적 특성 (Electrical Characteristic of PMMA Thin Film by Plasma Polymerization Method with Process Pressure and RF Substrate Bias Power)

  • 이붕주
    • 한국전자통신학회논문지
    • /
    • 제6권5호
    • /
    • pp.697-702
    • /
    • 2011
  • 본 논문에서는 유기박막트랜지스터용 절연막에 활용코자 플라즈마중합방법을 이용하여 PMMA 절연막을 제작하였다. 기판의 바이어스인가 및 증착중 압력변화에 따른 전기적특성을 파악한 결과, 플라즈마중합법에 의한 MMA절연막의 증착조건 RF100[W], Ar20[sccm], 5[mtorr], RF bias 20[W] 에서 3.4의 유전율, 8.6[nm/min]의 높은 증착율 및 높은 절연특성을 얻을수 있다. 이처럼 얻어진 플라즈마 중합막은 유기트랜지스터 및 유기메모리의 절연막으로 충분히 활용가능함을 알 수 있다.

The Synthesis of Cellulose-graft-poly (L-lactide) by Ring-opening Polymerization and the Study of Its Degradability

  • Dai, Lin;Xiao, Shu;Shen, Yue;Qinshu, Baichuan;He, Jing
    • Bulletin of the Korean Chemical Society
    • /
    • 제33권12호
    • /
    • pp.4122-4126
    • /
    • 2012
  • Cellulose-graft-poly (L-lactide) (cellulose-g-PLLA) was successfully prepared via ring-opening polymerization (ROP) by using 4-dimethylaminopyridine (DMAP) as an organic catalyst in an ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl). The structure and morphology of the polymer was characterized by nuclear magnetic resonance (NMR) and transmission electron microscope (TEM). From wide-angle X-ray powder diffraction (WAXD) and degradation test (by acid, alkaline, PBS and enzyme solution), changes in the crystalline structure as a result of degradation was also investigated. The results indicated that materials which have low degree of crystallinity showing higher degradability, however, in acid liquor, enzyme solution, alkaline liquor and PBS system, the degradation rate of the polymer decreased by the above sequence. Moreover, with the further increase of graft degree of this material, its degradation degree decreased.

환경친화적인 무기/유기 Core-Shell의 제조에 관한 연구 (A Study on the Environmental Fraternized Preparation of Inorganic/organic Core-shell Binder)

  • 설수덕;임재길;임종민;권재범;이내우
    • 한국안전학회지
    • /
    • 제19권1호
    • /
    • pp.81-87
    • /
    • 2004
  • Composite particles using inorganic and organic chemicals were synthesized and the results of those reaction were compared to variation of temperature and agitation speed in presence of $CaCO_3$ which was adsorbed SDBS. Also the synthesises were optimized according to conversion rate of composite particles. In inorganic/organic core-shell composite particle polymerization, $CaCO_3$ adsorbed by 0.5wt% surfactant SDBS was prepared initially and then core $CaCO_3$ was encapsulated by sequential emulsion polymerization using MMA at the addition of APS 3.16${\times}$$10^{-3}$mol/L to minimize the coagulated PMMA particle itself during MMA shell polymerization. Encapsulated PMMA on $CaCO_3$ as inorganic/organic core-shell particles was verified by FT-IR and DSC analysis. It was found that the $CaCO_3$ was very well encapsulated by PMMA as shell. The surfaces were distinctly found as spindle shape and broad particle distribution after capsulation.