• Title/Summary/Keyword: polymerization rate

Search Result 360, Processing Time 0.029 seconds

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

  • Kim, Hyoung-Sug;Kim, Kwan-Yung;Kang, Shin-Choon;Noh, Si-Tae;Kim, Jin-Seuk;Yu, Jae-Chul;Choi, Keun-Bae
    • Journal of the Korea Institute of Military Science and Technology
    • /
    • v.12 no.2
    • /
    • 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.

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
    • /
    • v.43 no.3
    • /
    • pp.157-165
    • /
    • 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.

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

  • Lim, Mi-Young;Cho, Kyung-Mo;Hong, Chan-Ui
    • Restorative Dentistry and Endodontics
    • /
    • v.32 no.1
    • /
    • pp.28-36
    • /
    • 2007
  • The purpose of this study was to compare the effect of exponential curing method with conventional curing and soft start curing method on polymerization shrinkage of composite resins. Three brands of composite resins (Synergy Duo Shade, Z250, Filtek Supreme) and three brands of light curing units (Spectrum 800, Elipar Highlight, Elipar Trilight) were used. 40 seconds curing time was given. The shrinkage was measured using linometer for 90 seconds. The effect of time on polymerization shrinkage was analysed by one-way ANOVA and the effect of curing modes and materials on polymerization shrinkage at the time of 90s were analysed by two-way ANOVA. The shrinkage ratios at the time of 20s to 90s were taken and analysed the same way. The results were as follows : 1. All the groups except Supreme shrank almost within 20s Supreme cured by soft start and exponential curing had no further shrinkage after 30s (p < 0.05). 2. Statistical analysis revealed that polymerization shrinkage varied among materials (p = 0.000) and curing modes (p = 0.003). There was no significant interaction between material and curing mode. 3. The groups cured by exponential curing showed the statistically lower polymerization shrinkage at 90s than the groups cured by conventional curing and soft start curing (p < 0.05). 4. The initial shrinkage ratios of soft start and exponential curing were statistically lower than conventional curing (p < 0.05). From this study, the use of low initial light intensities may reduce the polymerization rate and, as a result, reduce the stress of polymerization shrinkage.

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
    • /
    • v.2 no.2
    • /
    • 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

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

  • Ki Hyun Chung;Chwa Kyung Sung
    • Journal of the Korean Chemical Society
    • /
    • v.17 no.4
    • /
    • pp.298-305
    • /
    • 1973
  • Following results were obtained for the mechanical degradation of polystyrene (for polystyrene itself and when blended with rubber) by roll mastication. 1) The rate of mechanical degradation for polystyrene itself can be represented by the second-order rate equation proposed by Goto. $-\frac{dP_t}{dt} = k_s(P_t-P_{\infty})^2$ Where Pt is the degree of polymerization of the degraded polymer at t minutes and $P{\infty}$ is the final degree of polymerization. 2) The mechanical degradation of polystyrene component in the polystyrene-rubber (SBR, BR) blend system occurred similarly as that of polystyrene itself. 3) Under the experimental conditions the mechanical degradation rate of the polystyrene component of the polystyrene-rubber, (SBR, BR) blend system followed approximately the same second-order equation as that for polystyrene itself.

  • 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
    • /
    • v.31 no.5
    • /
    • 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
    • /
    • v.12 no.4
    • /
    • 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.

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

  • Lee, Boong-Joo
    • The Journal of the Korea institute of electronic communication sciences
    • /
    • v.6 no.5
    • /
    • pp.697-702
    • /
    • 2011
  • In this paper, We have fabricated PMMA thin films by plasma polymerization method for organic thin film transistor's insulator layer. In the electrical characteristic results with deposition pressures and substrate RF bias power in thin film deposition process, we have got dielectric constant of 3.4, high deposition rate of 8.6 [nm/min] and high insulation characteristics in condition of RF100 [W], Ar20 [sccm], 5 [mtorr], RF bias 20 [W]. Therefore, the fabricated thin films are possible as insulation layer of OTFT and organic memory.

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
    • /
    • v.33 no.12
    • /
    • 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.

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

  • Seoul, Soo-Duk;Lim, Jae-Keel;Lim, Jong-Min;Kwon, Jae-Beom;Lee, Nae-Woo
    • Journal of the Korean Society of Safety
    • /
    • v.19 no.1
    • /
    • 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.