• Title/Summary/Keyword: Radical polymerization

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A One-Component Negative Photoresist Based on an Epoxy Terpolymer Containing Oxime-Urethane Groups as a Photobase Generator

  • Chae, Kyu-Ho;Park, Jin-Hee
    • Macromolecular Research
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    • v.12 no.4
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    • pp.352-358
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    • 2004
  • For their application as one-component photoresists, we prepared epoxy terpolymers containing oxime-urethane and benzophenone groups by the radical polymerization of glycidyl methacrylate (GMA), metha-cryloxyethyl benzophenoneoxime urethane (MBU), and N-(4-benzoyl)phenylmaleimide (BPMI). The terpolymer composition was optimized to provide the most photosensitive photoresist. The photo-decomposition reaction of the oxime-urethane groups in the terpolymer was monitored by UV absorption spectroscopy, and the photo-crosslinking reaction of the epoxy terpolymer was observed by measuring the normalized thickness. The photosensitivity of the epoxy terpolymer increased as the amount of BPMI and MBU units increased up to 16 and 24 mol%, respectively. Among the terpolymers we prepared, terpolymer T-II(contents of GMA, MBU, BPMI are 75, 19, 6.1 mole%, respectively) exhibited the highest photosensitivity ( $D_{c}$ $^{0.5}$ = 430 mJ/$\textrm{cm}^2$) and had a moderate contrast (${\gamma}$$^{p}$ = 1.23). Negative-tone micropatterns having a line width of ca. 10 ${\mu}{\textrm}{m}$ were obtained by developing the system with chloroform.m.

Synthesis of Phosphoric Polymer Coating Solution with Antimicrobial Activity and Flame Retardant Efficiency (항균성과 난연성을 함유하고 있는 인계고분자 코팅용액의 합성)

  • Kim, Sang-Kyum;Lee, In-Soo;Seo, Sang-Hee;Choi, Seong-Ho
    • Polymer(Korea)
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    • v.35 no.5
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    • pp.431-437
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    • 2011
  • A polymeric coating solution based on poly(acryloyl diphosphoric acid)(poly(ADP)) was prepared via a radical polymerization of acryloyl diphosphoric acid using ammonium persulfate (APS) as an initiator in water at 70 $^{\circ}C$. The prepared polymeric coating solution exhibited significant antibacterial activity against salmonella typhimurium, pseudomonas aeruginosa, escherichia coli, and staphylococcus aureus. It also exhibited good antifungal activity against Asperigillus niger and good antiviral activity against the influenza (H1N1) virus. Additionally, it exhibited good flame retardant efficiency after applying it as a coating to a cotton fabric.

Influence of Quaternization on UCST Properties of Hydroxyl-Derivatized Polymers

  • Lee, Hyung-Il
    • Bulletin of the Korean Chemical Society
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    • v.35 no.10
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    • pp.3001-3004
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    • 2014
  • A series of hydroxyl-derivatized quaternized polymers were successfully synthesized by atom transfer radical polymerization (ATRP) and Cu(I)-catalyzed 1,3-dipolar cycloaddition of azide and alkynes (click chemistry), followed by quaternization reactions. ATRP was employed to synthesize poly(2-hydroxyethyl methacrylate) (PHEMA), followed by introduction of alkyne groups using pentynoic acid, leading to HEMA-Alkyne. 2-Azido-1-ethanol and 3-azido-1-propanol were combined with the HEMA-Alkyne backbone via click reaction, resulting in triazole-ring containing hydroxyl-derivatized polymers. Quaternization reactions with methyl iodide were conducted on the triazole ring of each polymer. Molecular weight, molecular weight distribution, and the degree of quaternization (DQ) were determined by gel permeation chromatography (GPC) and $^1H$ NMR spectroscopy. The average molecular weight ($M_n$) of the resulting polymers ranged from $5.9{\times}10^4$ to $1.05{\times}10^5g/mol$ depending on the molecular architecture. The molecular weight distribution was low ($M_w/M_n$ = 1.26-1.38). The transmission spectra of the 0.1 wt % aqueous solutions of the resulting quaternized polymers at 650 nm were measured as a function of temperature. Results showed that the upper critical solution temperature (UCST) could be finely controlled by the level of DQ.

Characterization and Rheological Properties of Dilute-solutions of Three Different Families of Water-soluble Copolymers Prepared by Solution Polymerization

  • Jimenez-Regalaso, Enrique Javier;Cadenas-Pliego, Gregorio;Perez-Alvarez, Marissa;Hernandez-Valdez, Yessica
    • Macromolecular Research
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    • v.12 no.5
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    • pp.451-458
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    • 2004
  • Water-soluble polyacrylamides hydrophobically modified with small amounts of N,N-dialkylacrylamides [N,N-dihexylacrylamide (DHAM) and N,N-dioctylacrylamide (DOAM)] have been prepared through free radical solution polymerizations using two hydrophobic initiators derived from 4,4' -azobis(4-cyanopentanoic acid) (ACVA) and long linear chains consisting of 12 and 16 carbon atoms (C12 and C16). This procedure resulted in polyacrylamides containing hydrophobic groups along the chain as well as at the chain ends. We compare the properties of this class of polymers, termed "combined associative polymers", with those of the multisticker (with hydrophobic groups along the polymer chain) and telechelic (with hydrophobic groups at the chain ends) associative polymers. These materials were prepared using DHAM or DOAM and a hydrophobic initiator (ACVA) modified with alkyl chains of two different lengths. Polymers having molecular weights (M$\_$w/) of ca. 175,000 and hydrophobic contents [H] of ca. 0.8 mol% were prepared using 0.07 mol% of initiator relative to the total monomer feed. We investigated the effects that the type, localization, and concentration of the hydrophobic groups have on the viscosities of the associative polymer solutions.

A Study on the Copolymerization Kinetics of Phenylethyl Acrylate and Phenylethyl Methacrylate

  • Lee, Han-Na;Tae, Gi-Yoong;Kim, Young-Ha
    • Macromolecular Research
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    • v.16 no.7
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    • pp.614-619
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    • 2008
  • Copolymers of phenyl alkyl acrylates/methacrylates are used clinically as soft materials for the foldable intraocular lens (IOL) to treat cataracts. In this study, copolymers of 2-phenylethyl acrylate (PEA) and 2-phenylethyl methacrylate (PEMA) of various compositions were prepared using free radical polymerization in solution. The composition of the copolymers was determined by $^1H$-NMR analysis. The reactivity ratios of the monomers were calculated using the conventional Fineman-Ross or Kelen-Tudos method. The reactivity ratio of PEA ($r_1$) and PEMA ($r_2$) were estimated to be 0.280 and 2.085 using the Kelen-Tudos method, respectively. These values suggest that PEMA is more reactive in copolymerization than PEA, and the copolymers will have a higher content of PEMA units. The glass transition temperature ($T_g$) of the copolymers increased with increasing PEMA content. The molecular weight and polydispersity indices ($M_w/M_n$) of the polymers were determined by GPC. Overall, these results are expected to be quite useful in applications to foldable soft IOL materials.

Preparation and Characterization of Proton Conducting Composite Membranes From P(VDF-CTFE)-g-PSPMA Graft Copolymer and Heteropolyacid

  • Seo, Jin-Ah;Roh, Dong-Kyu;Koh, Jong-Kwan;Kim, Jong-Hak
    • Korean Membrane Journal
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    • v.10 no.1
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    • pp.20-25
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    • 2008
  • Proton conducting composite membranes were prepared by solution blending of poly(vinylidene fluoride-co-chlorotrifluoroethylene)-graft-poly(sulfopropyl methacrylate) (P(VDF-CTFE)-g-PSPMA) graft copolymer and heteropolyacid (HPA). The P(VDF-CTFE)-g-PSPMA graft copolymer was synthesized by atom transfer radical polymerization (ATRP) using direct initiation of the secondary chlorines of P(VDF-CTFE). FT-IR spectroscopy revealed that HPA nanoparticles were incorporated into the graft copolymer via hydrogen bonding interactions. The water uptake of membranes continuously decreased with increasing HP A concentration up to 45wt%, after which it slightly increased. It is presumably due to the decrease in number of water absorption sites due to hydrogen bonding interaction between the HP A particles and the polymer matrix. The proton conductivity of membranes increased with increasing HPA concentration up to 45wt%, resulting from both the intrinsic conductivity of HP A particles and the enhanced acidity of the sulfonic acid of the graft copolymer.

Synthesis of Modified Silane Acrylic Resins and Their Physical Properties as Weather-Resistant Coatings

  • Yoo, Gyu-Yeol;Kim, Ji-Hyun;Park, Hong-Soo;Kim, Young-Geun;Kim, Seong-Kil
    • Journal of the Korean Applied Science and Technology
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    • v.25 no.1
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    • pp.1-14
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    • 2008
  • To prepare weather-resistant modified silane acrylic resin coatings for an architectural purpose, tetrapolymers were synthesized by radical polymerization. 3-Methacryloxypropyltrimethoxysilane (MPTS) as a silicone monomer and n-butyl acrylate, methyl methacrylate, and n-butyl methacrylate as acrylic monomers were used. The composition of monomers was adjusted to fix the glass transition temperature of acrylic polymer for $20^{\circ}C$. The composition of MPTS in the synthesized polymer were varied from 10 wt% to 30 wt%. On the basis of synthesized resin amber paints were prepared and their physical properties and effects on weatherability were examined. The presence of MPTS in modified silane acrylic resins generally resulted in low molecular weight and broad molecular weight distribution, and also lowered the viscosity of the copolymers. The coated films prepared from these resins showed good and balanced properties in general. Adhesion to the substrate was outstanding in particular. Weatherability tests were carried out in three different types such as outdoor exposure, QUV, and SWO. The test results showed that the modified silane acrylic resins containing 30 wt% of MPTS had superior weathering properties.

QMF Ion Beam System Development for Oxide Etching Mechanism Study (산화막 식각 기구 연구를 위한 QMF Ion Beam 장치의 제작)

  • 주정훈
    • Journal of the Korean institute of surface engineering
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    • v.37 no.4
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    • pp.220-225
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    • 2004
  • A new ion beam extraction system is designed using a simple ion mass filter and a micro mass balance and a QMS based detecting system. A quadrupole Mass Filter is used for selective ion beam formation from inductively coupled high density plasma sources with appropriate electrostatic lens and final analyzing QMS. Also a quartz crystal microbalance is set between a QMF and a QMS to measure the etching and polymerization rate of the mass selected ion beam. An inductively coupled plasma was used as a ion/radical source which had an electron temperature of 4-8 eV and electron density of $4${\times}$10^{11}$#/㎤. A computer interfaced system through 12bit AD-DA board can control the pass ion mass of the qmf by setting RF/DC voltage ratio applied to the quadrupoles so that time modulation of pass ion's mass is possible. So the direct measurements of ion - surface chemistry can be possible in a resolution of $1\AA$/sec based on the qcm's sensitivity. A full set of driving software and hardware setting is successfully carried out to get fundamental plasma information of the ICP source and analysed $Ar^{+}$ beam was detected at the $2^{nd}$ QMS.

Thermosensitive Block Copolymers Consisting of Poly(N-isopropylacrylamide) and Star Shape Oligo(ethylene oxide)

  • Lee, Seung-Cheol;Chang, Ji-Young
    • Bulletin of the Korean Chemical Society
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    • v.30 no.7
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    • pp.1521-1525
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    • 2009
  • Thermosensitive block copolymers of ethylene oxide and N-isopropylacrylamide (NIPAM) were synthesized. A five armed star shape oligo(ethylene oxide) initiator with a cyclotriphosphazene core was prepared and used for the atom transfer radical polymerization (ATRP) of NIPAM. The lower critical solution temperatures (LCSTs) of the copolymers were 36 to 46 ${^{\circ}C}$, higher than that of PNIPAM (32 ${^{\circ}C}$), depending on their molecular weights. The copolymers were soluble in water below the LCSTs but formed micelles above the LCSTs. The thermosensitive micellization behaviors of the polymers were investigated by fluorescence spectroscopy. With increasing the temperature of an aqueous solution of P2 and pyrene above the LCST, the peak of 333 nm red-shifted to appear around 339 nm and its intensity increased significantly, indicating the micelle formation. The transfer of pyrene into the micelles was also confirmed by a confocal laser scanning microscope. The fluorescence image obtained from P2 in an aqueous pyrene solution exhibited a green emission resulting from the pyrene transferred into the micelles. Salt effects on the solubility of the copolymers in an aqueous solution were investigated. The LCST of P2 decreased sharply as the concentration of sodium chloride increased, while decreased slowly with potassium chloride.

Synthesis and Swelling Kinetics of a Cross-Linked pH-Sensitive Ternary Copolymer Gel System (pH-민감성 삼성분계 공중합체 젤의 합성 및 팽윤 속도론)

  • Zafar, Zafar Iqbal;Malana, M.A.;Pervez, H.;Shad, M.A.;Momma, K.
    • Polymer(Korea)
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    • v.32 no.3
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    • pp.219-229
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    • 2008
  • A pH sensitive ternary copolymer gel was synthesized in the presence of ethylene glycol dimethacrylate (EGDMA) as a crosslinking agent through radical polymerization of vinyl acetate (VA), acrylic acid (AA) and methyl acrylate(MA) with a weight ratio of 1 : 1.3 : 1. A number of experiments were carried out to determine the swelling behavior of the gel under a variety of pH conditions of the swelling medium. As the pH of the swelling medium was changed from 1.0 to 8.0 at $37^{\circ}C$, the gel showed a shift in the pH-dependent swelling behavior from Fickian (n=0.3447) to non-Fickian (n=0.9125). The resulting swelling parameters were analyzed using graphical and statistical methods. The results showed that the swelling of the gel was controlled by the pH of the medium, i.e. $n=n_o{\exp}(S_{C}pH)$, where n is the diffusion exponent, $n_o(=28.9645{\times}10^{-2})$ is the pre-exponential factor and $S_C$(=0.1417) is pH sensitivity coefficient. The swelling behavior of the gel was also examined in aliphatic alcohols. The results showed that the rate of swelling increased with increasing number of carbon atoms in the alcoholic molecular chain.