• Macromolecular Research
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• 제15권2호
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• pp.109-113
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• 2007

The surface molecular motion of monodisperse polystyrene (PS) films was examined using scanning vis-coelasticity microscopy (SVM) in conjunction with lateral force microscopy (LFM). The dynamic storage modulus, E', and loss tangent, $tan\delta$, at a PS film surface with number-average molecular weights, $M_n$, smaller than 30 k were found to be smaller and larger than those for the bulk sample, even at room temperature, meaning that the PS surface is in a glass-rubber transition or fully rubbery sate at this temperature when the $M_n$ is small. In order to quantitatively elucidate the dynamics of the molecular motion at the PS surface, SVM and LFM measurements were performed at various temperatures. The glass transition temperature, $T_g$, at the surface was found to be markedly lower than the bulk $T_g$, and this discrepancy between the surface and bulk became larger with decreasing $M_n$. Such an intensive activation of the thermal molecular motion at the PS surfaces can be explained in terms of an excess free volume in the vicinity of the film surface induced by the preferential segregation of the chain end groups.

• Elastomers and Composites
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• 제28권4호
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• pp.267-273
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• 1993

A number of hydrophilic acrylic comonomers were incorporated into styrene-butadiene soap-free emulsion polymerization. It was found that reaction rate decreased according to : AN>AA>MMA>EA>IA>AAM>MA>HEMA. It was also observed that reaction rate increased with decreasing H-bonding factor contribution to the solubility parameter of the hydrophilic comonoer. The SBR latexes were very monodisperse with the particle size distribution of $1.03{\times}1.12$. Since growth rate is proportional to polymerization time, the difference in conversion rates between various comonomers was resulted from the particle number density of SBR latexes for the various hydrophilic comonomers. It was also found that the colloidal stability of the latexes was excellent because no external emulsifier was incorporated.

• Macromolecular Research
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• 제17권10호
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• pp.750-756
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• 2009

Stable, spherical, polystyrene particles were synthesized in ab initio dispersion polymerization by using the poly(methacrylic acid)[PMAA] macro-RAFT agent. The presence of the PMAA macro-RAFT agent on the polystyrene (PS) particles was confirmed by NMR and FTIR spectroscopy. The PS particle size was influenced by the concentration of the RAFT agent and monomer due to the initial nucleation. When the concentration of the PMAA macro-RAFT agent was increased from 2 to 10 wt% relative to the monomer, the average particle size decreased from 2.31 to 1.36 ${\mu}m$, the conversion decreased from 93.3 to 88.9%, the weight-average molecular weight increased from 46,300 to 150,200 g $mol^{-1}$ and the PDI decreased from 2.79 to 1.94, respectively. In particular, the incorporation of 10 wt% of PMAA macro-RAFT agent produced monodisperse PS spheres of 1.36 ${\mu}m$ with a coefficient of variation (CV) of 6.44%. Thus, the PMAA macro-RAFT agent worked as a reactive steric stabilizer providing monodisperse, micron-sized, PS particles.

• Korea-Australia Rheology Journal
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• 제18권4호
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• pp.199-207
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• 2006

Measurements by Luap et al. (2005) of elongational viscosity and birefringence of two nearly monodisperse polystyrene melts with molar masses $M_{w}$ of $206,000g{\cdot}mol^{-1}$ (PS206k) and $465,000g{\cdot}mol^{-1}$ (PS465k) respectively are reconsidered. At higher elongational stresses, the samples showed clearly deviations from the stress optical rule (SOR). The elongational viscosity data of both melts can be modeled quantitatively by the MSF model of Wagner et al. (2005), which is based on the assumption of a strain-dependent tube diameter and the interchain pressure term of Marrucci and Ianniruberto (2004). The only nonlinear parameter of the model, the tube diameter relaxation time, scales with $M_{w}^{2}$. In order to get agreement with the birefringence data, finite chain extensibility effects are taken into account by use of the $Pad\'{e}$ approximation of the inverse Langevin function, and the interchain pressure term is modified accordingly. Due to a selfregulating limitation of chain stretch by the FENE interchain pressure term, the transient elongational viscosity shows a small dependence on finite extensibility only, while the predicted steady-state elongational viscosity is not affected by non-Gaussian effects in agreement with experimental evidence. However, deviations from the SOR are described quantitatively by the MSF model by taking into account finite chain extensibility, and within the experimental window investigated, deviations from the SOR are predicted to be strain rate, temperature, and molar mass independent for the two nearly monodisperse polystyrene melts in good agreement with experimental data.

• 접착 및 계면
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• 제13권3호
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• pp.101-108
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• 2012

음이온개시제인 $K_2S_2O_8$ (KPS)와 양이온개시제인 2,2' azobis(2-methyl-propionamidine) dihydrochloride (AIBA)를 이용하여 MMA와 BMA 단량체간의 무유화공중합을 성공적으로 수행하여 PSD가 1.002~1.008인 단분산성이 우수한 poly(BMA-co-MMA)와 PBMA 라텍스들을 제조하였다. 실험결과, 160~494 nm 범위의 수평균입자경과 (1.25~7.55) ${\times}10^4$ 범위의 수평균분자량을 나타내었다. MMA/BMA 유화중합에 따르는 중합속도와 단량체 및 개시제 농도, DVB/EGDMA 가교제 농도, 중합온도 변화에 따르는 수평균입자경과 수평균분자량의 영향을 조사하였다. MMA/BMA 단량체 중 MMA 농도가 증가함에 따라 중합속도가 증가하였으며 일반적으로 이들 라텍스의 평균입자경과 평균분자량은 MMA/BMA 단량체중량비, 단량체량, 개시제량, 중합온도에 따라 쉽게 조절됨을 발견하였다.

• 접착 및 계면
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• 제13권3호
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• pp.109-115
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• 2012

2단계 유화중합에 의한 단분산의 블루칼라 착색 poly(styrene-co-acrylic acid) 라텍스를 성공적으로 제조하였다. 0.21 ${\mu}m$의 polystyrene 시드를 이용하여 중합 2단계에서 Blue 606 염료와 acrylic acid의 중합으로 carboxyl 음이온을 갖는 블루칼라 라텍스를 합성하였다. 본 연구에서 제조한 블루칼라 라텍스는 모두 1.01 이하의 우수한 단분산도를 가지며 0.25~0.42 ${\mu}m$ 범위의 입자경을 나타내었다. 중합 2단계에서 acrylic acid 부가시간이 늘어남에 따라 입자경은 증가하였고 30 min 이상으로 늘어남에 따라 콜로이드 안정성을 갖는 블루칼라 라텍스가 제조되었다. 20 wt% AA 농도에서 -145 mV의 제타전위와 $-9.4{\times}10^{-6}\;cm^2/Vs$의 전기영동이동도를 나타내었다. 25 wt% DVB 농도하에서 396.7 K의 높은 유리전이온도를 나타내었다.

• 한국고분자학회:학술대회논문집
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• 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
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• pp.86-88
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• 2006

The novel linear- (V-LUM) and cross-type macromonomers (C-VUM) of vinyl-terminated bifunctional polyurethane were synthesized and applied to the dispersion polymerization of styrene and MMA in ethanol. The existence of the vinyl terminal groups and the grafted macromonomer with styrene and PMMA was verified using 1H NMR and 13C NMR. Monodisperse polystyrene (PS) microspheres were successfully obtained above 15 wt % of macromonomer relative to styrene. The macromonomer can efficiently stabilize higher surface area of the particles compared to a conventional stabilizer, PVP. The grafting ratio of the PS calculated from 1H NMR linearly increased up to 0.048 with 20 wt % of the macromonomer and the high molecular weights (501,300 g/mol) of PS with increased glass transition and enhanced thermal stability were obtained. Furthermore, the stable and monodisperse PMMA microspheres having a weight-average diameter of $5.09{\mu}m$ and a good uniformity of 1.01 were obtained with 20 wt% L-VUM. The molecular weight increased, but the size of the PMMA particles decreased with the macromonomer concentration due to the increased stabilizing effect. The molecular weight of the PMMA was approximately two fold higher than that by a conventional PVP. The L-VUM acts as a reactive stabilizer, which gives polyurethane-grafted PS or PMMA with a high molecular weight. In addition, the XPS result showed that the C-PS (PS using the C-VUM) was anchored with a larger amount of PEG than that of the L-PS (PS using the L-VUM) on the particle surface. Thus, the reaction and stabilizing mechanism of the macromonomers for the formation of PS particles is proposed.

• Elastomers and Composites
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• 제49권3호
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• pp.232-238
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• 2014

수용성 단량체인 아크릴산 (AA)을 단량체로 potassium persulfate (KPS)를 개시제로 이용하여 $60^{\circ}C$에서 $90^{\circ}C$ 사이의 선택된 온도에서 물을 반응매체로 하여 용액중합을 진행하였다. 아크릴산의 농도가 감소하거나 개시제의 농도가 증가하면 분자량은 감소하였다. 중합반응온도를 상승하면 폴리아크릴산 (PAA)의 분자량은 감소하였다. 대부분의 중합반응에서 분산성지수는 1.5 에 근접하는 것으로 관찰되었다. 교반속도가 증가하면서 400 rpm에서 분자량은 최고값을 나타낸 후, 교반속도가 800 rpm에 이르면서 수평균 및 중량평균분자량은 감소하였다. 유리전이온도는 분자량에 따라 크게 변하지 않았으며 $113^{\circ}C$에서 $116^{\circ}C$ 사이의 값을 나타내었다.

• Bulletin of the Korean Chemical Society
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• 제31권7호
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• pp.1891-1896
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• 2010

Submicron-sized polymeric colloidal particles can self assemble into 3-dimensional (3D) opal structure which is a useful template for photonic crystal. Narrowly dispersed polymer microspheres can be synthesized by emulsion polymerization in water using water-soluble radical initiator. In this report, we demonstrate a facile and reproducible emulsion polymerization method to prepare various polymeric microspheres within 200 - 400 nm size ranges which can be utilized as colloidal photonic crystal template. By controlling the amount of monomer and surfactant, monodisperse polymer colloids of polystyrene (PS) and acrylates with various sizes were successfully prepared without complicated synthetic procedures. Such polymer colloids self-assembled into 3D opal structure exhibiting bright colors by reflection of visible light. The colloidal particles and the resulting opal structures were rigorously characterized, and the wavelength of the structural color from the colloidal crystal was confirmed to have quantitative relationship with the size of constituting colloidal particles as predicted by Bragg equation. The tunability of the structural color was achieved not only by varying the particle size but also by infiltration of the colloidal crystal with liquids having different refractive indices.

• Biotechnology and Bioprocess Engineering:BBE
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• 제11권3호
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• pp.179-186
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• 2006

End-Labeled Free-Solution Electrophoresis (ELFSE) is a new technique that is a promising bioconjugate method for DNA sequencing (or separation) and genotyping by both capillary and microfluidic device electrophoresis. Because ELFSE enables high-resolution electrophoretic separation in aqueous buffer alone (i.e., without a polymer matrix), it eliminates the need to load viscous polymer networks into electrophoresis microchannels. To achieve microchannel DNA separations with high performance, ELFSE requires monodisperse perturbing entities (i.e., drag-tags), which create a large amount of frictional drag when pulled behind DNA during free-solution electrophoresis, and which have other properties suitable for microchannel electrophoresis. In this article, the theoretical concepts of ELFSE and the required characteristics of the drag-tag molecules for the ultimate performance of ELFSE are reviewed. Additionally, the merits and limitations of current drag-tags are also discussed in the context of recent experimental data of ELFSE separation (or sequencing).