• Title/Summary/Keyword: chain transfer to polymer

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Polymerization and Application of Contact Lens Materials (콘택트렌즈 재료의 합성과 응용에 관한 연구)

  • Song, Kyung-Sek;Lee, Jong-Heon;Sung, A-Young
    • Journal of Korean Ophthalmic Optics Society
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    • v.8 no.2
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    • pp.129-134
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    • 2003
  • A wide variety of unsaturated vinyl derivatives can be induced to undergo free-radical chain polymerization. The capability to carry out a thermodynamically feasible polymerization relies on its kinetic feasibility on whether the proceeds at a reasonable rate under a given set of reaction conditions. Initiator or promoter is often required to achieve the kinetic feasibility. Only a few unsaturated monomers including methyl methacrylate(MMA) are known to absorb light between 250 and 500 nm which is the most convenient wavelength range. Also, the polysilanes with unusual optical and electronic properties have been used as ceramic precursors, deep UV photoresists, photoconductors. The hydrosilation has been used to make many interesting types of silicon containing polymers such as copolymer, dendrimers. Bulk polymerization of monomers with different molar radio of hydrosilanes(9:1 through 1:9) were performed. A quartz test tube charged with monomer and hydrosilane was degassed and irradiated with 250 nm UV for 6 hours. The polymer was taken in toluene, precipitated in hexane, filtered off, and dried. It was found that the initiators appeared to competitively and concurrently function as both chain initiation and transfer agents in the polymerization of vinyl monomers.

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Effect of Solvent Content on Morphology and Rubber Particle Size Distribution of High Impact Polystyrene (용매 함량이 내충격성 폴리스티렌의 형태구조 및 고무 입도분포에 미치는 영향)

  • 정한균;박정신;장대석;이성재
    • Polymer(Korea)
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    • v.26 no.3
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    • pp.307-315
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    • 2002
  • Major factors affecting the impact resistance of high impact polystyrene (HIPS), the rubber-toughened grade of polystyrene, are rubber-phase particle size and size distribution, molecular weight, morphology, and degree of grafting. Accordingly, it is important to control or investigate these factors. In this study, the effect of solvent content was analyzed by the morphology and particle size distribution of rubber phase, and final properties in bulk-solution polymerization of HIPS. The prepolymerization time was, first, determined by measuring the evolution of particle size distribution of dispersed phase to explain the phase inversion with time. As the solvent content increased, the size of rubber particle increased and then gradually decreased. Rubber-phase morphology was likely to have higher degree of grafting as the solvent content increased. Rheological and mechanical properties decreased as the solvent content increased because of the decrease of matrix molecular weight due to the chain transfer reaction to solvent and the existence of residual solvent. Nevertheless, the impact resistance seemed to increase when the rubber particle size increased.

Structural Changes in Isothermal Crystallization Processes of Synthetic Polymers Studied by Time-Resolved Measurements of Synchrotron-Sourced X-Ray Scatterings and Vibrational Spectra

  • Tashiro, Kohji;Hama, Hisakatsu
    • Macromolecular Research
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    • v.12 no.1
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    • pp.1-10
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    • 2004
  • The structural changes occurring in the isothermal crystallization processes of polyethylene (PE), poly-oxymethylene (POM), and vinylidene fluoridetrifluoroethylene (VDFTrFE) copolymer have been reviewed on the basis of our recent experimental data collected by the time-resolved measurements of synchrotron-sourced wide-angle (WAXS) and small-angle X-ray scatterings (SAXS) and infrared spectra. The temperature jump from the melt to a crystallization temperature could be measured at a cooling rate of 600-1,000 $^{\circ}C$/min, during which we collected the WAXS, SAXS, and infrared spectral data successfully at time intervals of ca. 10 sec. In the case of PE, the infrared spectral data clarified the generation of chain segments of partially disordered trans conformations immediately after the jump. These segments then became transformed into more-regular all-trans-zigzag forms, followed by the formation of an orthorhombic crystal lattice. At this stage, the generation of a stacked lamella structure having an 800-${\AA}$-long period was detected in the SAXS data. This structure was found to transfer successively to a more densely packed lamella structure having a 400-${\AA}$-long period as a result of the secondary crystallization of the amorphous region in-between the original lamellae. As for POM, the formation process of a stacked lamella structure was essentially the same as that mentioned above for PE, as evidenced from the analysis of SAXS and WAXS data. The observation of morphology-sensitive infrared bands revealed the evolution of fully extended helical chains after the generation of lamella having folded chain structures. We speculate that these extended chains exist as taut tie chains passing continuously through the neighboring lamellae. In the isothermal crystallization of VDFTrFE copolymer from the melt, a paraelectric high-temperature phase was detected at first and then it transferred into the ferroelectric low-temperature phase at a later stage. By analyzing the reflection profile of the WAXS data, the structural ordering in the high-temperature phase and the ferroelectric phase transition to the low-temperature phase of the multi-domain structure were traced successfully.

Synthesis of High Molecular Weight Poly(vinyl alcohol) by Low Temperature Polymerization of Vinyl Acetate in Tertiary Butyl Alcohol and the Following Saponification (아세트산비닐의 삼차부틸알코올계 저온 중합 및 비누화에 의한 고분자량 폴리비닐알코올의 합성)

  • 류원석;한성수;최진현;유상우;홍성일
    • Polymer(Korea)
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    • v.24 no.5
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    • pp.610-620
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    • 2000
  • Vinyl acetate (VAc) was polymerized at 30, 40, and 5$0^{\circ}C$ using 2,2'-azobis (2,4-dimethylvaleronitrile) (ADMVN) and tertiary butyl alcohol (TBA) as the initiator and the solvent, respectively. High molecular weight (HMW) atactic poly(vinyl alcohol) (PVA) was prepared by saponifying the poly(vinyl acetate) (PVAc) synthesized. The effect of polymerization conditions were investigated in terms of conversion, degree of branching for acetyl group of PVAc, and molecular weight of both PVAc and PVA. The polymerization rate of VAc in TBA was proportional to the 0.49th power of ADMVN concentration in good accordance with the theoretical value of 0.5. HMW-PVA with high yield could be obtained successfully, probably due to lower polymerization temperature and decreased chain transfer reaction rate which was achieved by adopting ADMVN and TBA. PYAc having average degree of polymerization (P$_{n}$) of 10000~13000 was obtained at the conversion of 35~70%. Saponification of so prepared PVAc yielded PVA having P$_{n}$ of 2400~6100. The syndiotactic diad content increased with decreasing polymerization temperature and increasing VAc concentration due to a steric hindrance effect of TBA during polymerization.

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Hydrophilic property by contact angle change of ion implanted polycarbonate (이온주입 Polycarbonate의 접촉각 변화에 의한 친수특성)

  • Lee, Chan-Young;Lee, Jae-Hyung;Lim, Kee-Joe
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2003.11a
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    • pp.533-538
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    • 2003
  • It has been shown that ion implantation produces remarkable improvements in surface-sensitive physical and chemical properties as well as other mechanical properties, in polymers. In this study, ion implantation was performed onto polymer, PC(polycarbonate), in order to investigate surface hydrophilic property through contact angle measurement using distilled water. PC was irradiated with N, Ar, Xe ions at the irradiation energy of $20\;{\sim}\;50keV$ and the dose range of $5{\times}10^{15},\;1{\times}10^{16},\;7{\times}10^{16}\;ions/cm^2$. The contact angle of water has been reduced with increasing fluence and ion mass but increased with increasing implanted energy. The changes of chemical and structural property are discussed in view of infrared spectroscopy and FT-IR, XPS, which shows increasing C-O bonding and C-C bonding. The root mean square of surface roughness examined by means of AFM changed smoothly from 0.387nm to 0.207nm and the change of wettability was discussed with respect to elastic and inelastic collisions obtained as results of TRIM simulation. It was found that wettability of the modified PC surface was affected on change of functional group and nuclear stopping or linear energy transfer(LET, energy deposited per unit track length per ion) that causes chain scission by displacing atom from polymer chains, but was not greatly dependant on surface morphology.

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Synthesis and Characterization of Iridium-Containing Green Phosphorescent Polymers for PLEDs

  • Xu, Fei;Kim, Hee Un;Mi, Dongbo;Lim, Jong Min;Hwang, Ju Hyun;Cho, Nam Sung;Lee, Jeong-Ik;Hwang, Do-Hoon
    • Bulletin of the Korean Chemical Society
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    • v.34 no.2
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    • pp.399-405
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    • 2013
  • Two series of new green phosphorescent polymers bearing a bis(2-phenyl-pyridine)iridium(III)(dibenzoylmethane) [$(ppy)_2Irdbm$] complex were designed and synthesized. Poly-carbazole (PCbz) derivative or polyfluorene with pendant carbazole groups (PFCbz) were employed as host polymers for the iridium complex. The iridium complex monomer was copolymerized with the host monomers using varying monomer ratios via a Yamamoto coupling reaction. Efficient energy transfer from host to dopant unit was observed by increasing the ratio of the iridium guest in the copolymers. Electroluminescent devices with the configuration ITO/PEDOT:PSS/polymer/BmPyPB/LiF/Al were fabricated and characterized. The phosphorescent polymers composed of the iridium complex guest and polyfluorene with carbazole pendants as a host performed better than the polymers composed of the same guest and the main chain polycarbazole host. A maximum external quantum efficiency of 0.73%, a luminous efficiency of 1.21 cd/A, and a maximum luminance of 372 $cd/m^2$ were obtained from a device fabricated using one of the synthesized copolymers.

Synthesis and Thermo-responsive Properties of Amino Group Terminated Poly(N-isopropylacrylamide) and Sodium Alginate-g-Poly(N-isopropylacrylamide) (말단 아민기를 갖는 폴리(N-이소프로필아크릴아미드) 및 알긴산 나트륨-g-폴리(N-이소프로필아크릴아미드)의 합성과 열응답 특성)

  • Lee, Eun Ju;Kim, Young Ho
    • Polymer(Korea)
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    • v.37 no.4
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    • pp.539-546
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    • 2013
  • Amino group-terminated poly(N-isopropylacrylamide) (PNIPAAm-$NH_2$) was synthesized via a radical polymerization of N-isopropylacrylamide (NIPAAm) using 2-aminoethanethiol hydrochloride (AESH) as a chain transfer agent. The molecular weight of the PNIPAAm-$NH_2$ was controlled by changing the concentration of AESH. The LCST of the aqueous solution of PNIPAAm-$NH_2$ increased slightly with increasing the AESH concentration. Alginate-g-PNIPAAm copolymer was synthesized by grafting PNIPAAm-$NH_2$ onto sodium alginate using N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide and N-hydroxysuccinimide. The formation of the grafted copolymers was confirmed by FTIR spectroscopy, solubility in water, and SEM-EDS. Alginate-g-PNIPAAm also exhibited swelling-deswelling behavior. However, it showed a LCST at a slightly increased temperature compared to PNIPAAm. The swelling ratio of the alginate-g-PNIPAAm hydrogel increased with the increase of the grafted PNIPAAm content.

Perfluoropolymer Membranes of Tetrafluoroethylene and 2,2,4Trifluofo- 5Trifluorometoxy- 1,3Dioxole.

  • Arcella, V.;Colaianna, P.;Brinati, G.;Gordano, A.;Clarizia, G.;Tocci, E.;Drioli, E.
    • Proceedings of the Membrane Society of Korea Conference
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    • 1999.07a
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    • pp.39-42
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    • 1999
  • Perfluoropolymers represent the ultimate resistance to hostile chemical environments and high service temperature, attributed to the presence of fluorine in the polymer backbone, i.e. to the high bond energy of C-F and C-C bonds of fluorocarbons. Copolymers of Tetrafluoroethylene (TEE) and 2, 2, 4Trifluoro-5Trifluorometoxy- 1, 3Dioxole (TTD), commercially known as HYFLON AD, are amorphous perfluoropolymers with glass transition temperature (Tg)higher than room temperature, showing a thermal decomposition temperature exceeding 40$0^{\circ}C$. These polymer systems are highly soluble in fluorinated solvents, with low solution viscosities. This property allows the preparation of self-supported and composite membranes with desired membrane thickness. Symmetric and asymmetric perfluoropolymer membranes, made with HYFLON AD, have been prepared and evaluated. Porous and not porous symmetric membranes have been obtained by solvent evaporation with various processing conditions. Asymmetric membranes have been prepared by th wet phase inversion method. Measure of contact angle to distilled water have been carried out. Figure 1 compares experimental results with those of other commercial membranes. Contact angles of about 120$^{\circ}$for our amorphous perfluoropolymer membranes demonstrate that they posses a high hydrophobic character. Measure of contact angles to hexandecane have been also carried out to evaluate the organophobic character. Rsults are reported in Figure 2. The observed strong organophobicity leads to excellent fouling resistance and inertness. Porous membranes with pore size between 30 and 80 nanometers have shown no permeation to water at pressures as high as 10 bars. However high permeation to gases, such as O2, N2 and CO2, and no selectivities were observed. Considering the porous structure of the membrane, this behavior was expected. In consideration of the above properties, possible useful uses in th field of gas- liquid separations are envisaged for these membranes. A particularly promising application is in the field of membrane contactors, equipments in which membranes are used to improve mass transfer coefficients in respect to traditional extraction and absorption processes. Gas permeation properties have been evaluated for asymmetric membranes and composite symmetric ones. Experimental permselectivity values, obtained at different pressure differences, to various single gases are reported in Tab. 1, 2 and 3. Experimental data have been compared with literature data obtained with membranes made with different amorphous perfluoropolymer systems, such as copolymers of Perfluoro2, 2dimethyl dioxole (PDD) and Tetrafluorethylene, commercialized by the Du Pont Company with the trade name of Teflon AF. An interesting linear relationship between permeability and the glass transition temperature of the polymer constituting the membrane has been observed. Results are descussed in terms of polymer chain structure, which affects the presence of voids at molecular scale and their size distribution. Molecular Dyanmics studies are in progress in order to support the understanding of these results. A modified Theodoru- Suter method provided by the Amorphous Cell module of InsightII/Discover was used to determine the chain packing. A completely amorphous polymer box of about 3.5 nm was considered. Last but not least the use of amorphous perfluoropolymer membranes appears to be ideal when separation processes have to be performed in hostile environments, i.e. high temperatures and aggressive non-aqueous media, such as chemicals and solvents. In these cases Hyflon AD membranes can exploit the outstanding resistance of perfluoropolymers.

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Preparation and characterization of Poly(2-methacryloyloxyethyl phosphorylcholine/fluorescein O-methacrylate)-coated iron oxide nanoparticles (Poly(2-methacryloyloxyethyl phosphorylcholine/fluorescein O-methacrylate)가 도입된 산화철 나노 입자의 제조 및 발열 특성 연구)

  • Ryu, Sunggon;Cheong, In Woo
    • Journal of Adhesion and Interface
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    • v.19 no.3
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    • pp.106-112
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    • 2018
  • Recently, the hyperthermia treatment of malignant tissues has gained great attention as a biocompatible and benign method that facilitates successful cancer therapy compared to radiation and chemotherapy. In this study, superparamagnetic ($Fe_3O_4$) iron oxide nanoparticles (IONP) coated with biocompatible polymer (IONP@P(MPC/FOM)) for the purpose of hyperthermia treatment were prepared and related characterization were performed. IONPs with having 15 nm diameter were first prepared by coprecipitation and followed by surface modification with 4-cyanopentanoic acid dithiobenzoate (CTP) for reversible addition-fragmentation chain transfer (RAFT) copolymerization by using 2-methacryloyloxyethyl phosphorylcholine (MPC) and fluorescein O-methacrylate (FOM) to form corona layer of P(MPC/FOM) on the surface of the IONP. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) confirmed the morphology and hydrodynamic size of the IONP@P(MPC/FOM) and thermogravimetric analysis (TGA) confirmed the formation of P(MPC/FOM) corona layer, respectively. Exposing IONP dispersion to alternating magnetic field suggests that the IONP@P(MPC/FOM) aqueous dispersion with 0.2 wt.% can be used for hyperthermia treatment.

Solvent-Polymer Interactions for Stable Non-Aqueous Graphene Dispersions in the Presence of PVK-b-PVP Block Copolymer (PVK-b-PVP 블록 공중합체의 존재 하에서 안정한 비 수계 그래핀 분산액을 위한 용매-고분자 상호작용에 관한 연구)

  • Park, Kyung Tae;Perumal, Suguna;Lee, Hyang Moo;Kim, Young Hyun;Cheong, In Woo
    • Journal of Adhesion and Interface
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    • v.18 no.3
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    • pp.109-117
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    • 2017
  • Poly(N-vinyl carbazole) (PVK) homopolymer, poly(4-vinylpyridine) (PVP) homopolymer, and PVK-b-PVP block copolymer were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization and the polymers were used to prepare non-aqueous graphene dispersions with four different solvents, ethanol, N-methyl-2-pyrrolidone (NMP), dichloromethane (DCM), and tetrahydrofuran (THF). $^1H-$ and $^{13}C-NMR$ spectroscopy, size exclusion chromatography (SEC), and differential scanning calorimetry (DSC) were carried out to confirm the chemical structure of the polymers. Stability of graphene dispersions was measured by on-line turbidity measurement. Time-dependent Turbiscan Stability Index (TSI) values were interpreted in terms of surface tension (${\sigma}$) and solubility parameter (${\delta}$) among solvents, polymers, and graphene. It was confirmed that the solubilities of polymer and surface tension between solvent and graphene affected the dispersion stability of graphene. PVK-b-PVP block copolymer could effectively maintain the low TSI values of graphene dispersions in ethanol and THF, which have been known as poor solvents for graphene dispersions. It can also be noted that DCM shows good dispersion stability comparable to NMP, which has been known as the best solvent for graphene dispersion.