• Title/Summary/Keyword: free-radical polymerization

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Synthesis of Copolymers Composed of 1H,1H,2H,2H-perfluorodecylmethacrylate and tert-butylmethacrylate and Their Lithographic Properties in Carbon Dioxide (1H,1H,2H,2H-퍼플로로데실메타크릴레이트와 tert-부틸메타크릴레이트로 구성된 공중합체의 합성 및 이산화탄소에서의 리소그라피 특성에 관한 연구)

  • Hwang, Ha Soo;Lee, Jin-kyun;Park, In;Huh, Hoon;Lim, Kwon Taek
    • Applied Chemistry for Engineering
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    • v.19 no.4
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    • pp.402-406
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    • 2008
  • A series of random copolymers, composed of 1H,1H,2H,2H-perfluoro decyl methacrylate (FDMA) as a $CO_2$-philic monomer and tert-butyl methacrylate (TBMA) as an acid labile monomer, were synthesized by free radical polymerization. The solubility of copolymers in carbon dioxide, light sensitivity at 365 nm exposure, and photoresist pattern formation properties were investigated. Furthermore, sub micron-sized poly(styrenesulfonate) : poly(3,4-ethylenedioxythiophene) (PSS : PEDOT) conducting polymer patterns were successfully prepared by pattern transfer.

Partially Hydrolyzed Crosslinked Alginate-graft-Polymethacrylamide as a Novel Biopolymer-Based Superabsorbent Hydrogel Having pH - Responsive Properties

  • Pourjavadi A.;Amini-Fazi M. S.;Hosseinzadeh H.
    • Macromolecular Research
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    • v.13 no.1
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    • pp.45-53
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    • 2005
  • In this study, a series of highly swelling hydrogels based on sodium alginate (NaAlg) and polymethacryl­amide (PMAM) was prepared through free radical polymerization. The graft copolymerization reaction was performed in a homogeneous medium and in the presence of ammonium persulfate (APS) as an initiator and N,N'-methylenebis­acrylamide (MBA) as a crosslinker. The crosslinked graft copolymer, alginate-graft-polymethacrylamide (Alg-g­PMAM), was then partially hydrolyzed by NaOH solution to yield a hydrogel, hydrolyzed alginate-graft-poly­methacrylamide (H-Alg-g-PMAM). During alkaline hydrolysis, the carboxamide groups of Alg-g-PMAM were converted into hydrophilic carboxylate anions. Either the Alg-g-PMAM or the H-Alg-g-PMAM was characterized by FTIR spectroscopy. The effects of the grafting variables (i.e., concentration of MBA, MAM, and APS) and the alkaline hydrolysis conditions (i.e., NaOH concentration, hydrolysis time, and temperature) were optimized systematically to achieve a hydrogel having the maximum swelling capacity. Measurements of the absorbency in various aqueous salt solutions indicated that the swelling capacity decreased upon increasing the ionic strength of the swelling medium. This behavior could be attributed to a charge screening effect for monovalent cations, as well as ionic cross-linking for multivalent cations. Because of the high swelling capacity in salt solutions, however, the hydrogels might be considered as anti-salt superabsorbents. The swelling behavior of the superabsorbing hydrogels was also measured in solutions having values of pH ranging from 1 to 13. Furthermore, the pH reversibility and on/off switching behavior, measured at pH 2.0 and 8.0, suggested that the synthesized hydrogels were excellent candidates for the controlled delivery of bioactive agents. Finally, we performed preliminary investigations of the swelling kinetics of the synthesized hydrogels at various particle sizes.

Syntheses of Alternating Head-to Head Vinyl Copolymers and Vinyl Terpolymers via Ring-Opening Mechanism. Ring-Opening Polymerization of Substituted-3,4-dihydro-2H-pyrans

  • Lee, Ju-Yeon;Cho, I-Whan
    • Bulletin of the Korean Chemical Society
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    • v.8 no.2
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    • pp.96-101
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    • 1987
  • 2-Ethoxy-6-methoxy-5-cyano-3,4-dihydro-2H-pyran (1_a$), 2-n-butoxy-6-methoxy-5-cyano-3,4-dihydro-2H-pyr an (1b), 2-isobutoxy-6-methoxy-5-cyano-3,4-dihydro-2H-py ran ($1_c$), and 2-ethoxy-6-methoxy-3-methyl-5-cyano-3,4-dihydro -2H-pyran ($1_d$) were prepared by (4 + 2) cycloaddition reaction of methyl $\alpha$-cyanoacrylate with the corresponding alkyl vinyl ethers. Compounds $1_{a-d}$ were ring-open polymerized by cationic catalyst to obtain alternating head-to-head (H-H) copolymers. For comparison, head-to-tail (H-T) copolymer $3_a$ was also prepared by free radical copolymerization of the corresponding monomers. The H-H copolymer exhibited minor differences in its $1_H% NMR and IR spectra, but in the $^{13}C$ NMR spectra significant differences were observed between the H-H and H-T copolymers. Glass transition temperature ($T_g$) of H-H copolymer was higher than that of the H-T copolymer, but thermal decomposition temperature of the H-H copolymer was lower than that of the H-T copolymer. Compounds $1_a$, $a_b$, and $1_c$, copolymerized well with styrene by cationic catalyst, but compound 1d failed to copolymerize with styrene. All of the H-H and H-T copolymers were soluble in common solvents and the inherent viscosities were in the range 0.2-0.4 dl/g.

Synthesis of Starch-g-PAN Polymer Electrolyte Membrane and Its Application to Flexible Solid Supercapacitors (Starch-g-PAN 고분자 전해질막 합성 및 플렉서블 고체 슈퍼 캐퍼시터 응용)

  • Min, Hyo Jun;Jung, Joo Hwan;Kang, Miso;Kim, Jong Hak
    • Membrane Journal
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    • v.29 no.3
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    • pp.164-172
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    • 2019
  • In this work, we demonstrate a facile process to prepare an electrolyte membrane for the supercapacitor based on a graft copolymer consisting of starch and poly(acrylonitrile) (PAN). The graft copolymer (starch-g-PAN) was synthesized via free radical polymerization initiated by ceric ions. The starch-g-PAN was dissolved in ionic liquid, i.e. 1-ethyl-3-methylimidazolium dicyanamide (EMIM DCA) without any organic solvents at room temperature. The gelation of polymer electrolyte membranes occurred by applying high temperature, i.e. $100^{\circ}C$ for 1 hour. The resultant electrolyte membrane was flexible and thus applied to flexible solid supercapacitors. The performance of the supercapacitor based on starch-g-PAN graft copolymer electrolyte reached 21 F/g at a current density of 0.5 A/g. The cell also showed high cyclic stability with 86% of retention rate within 10,000 cycles. The preparation of starch-g-PAN based polymer electrolyte membrane provides opportunities for facile fabrication of flexible solid supercapacitors with good performance.

Highly Efficient Production of Monodisperse Poly(ethylene glycol) (PEG) Hydrogel Microparticles by Utilizing Double Emulsion Drops with a Sacrificial Thin Oil Shell (얇은 오일쉘 이중에멀젼을 이용한 고효율 단분산성 하이드로젤 마이크로 입자 생산)

  • Kim, Byeong-Jin;Jeong, Hye-Seon;Choi, Chang-Hyung
    • Korean Chemical Engineering Research
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    • v.60 no.1
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    • pp.139-144
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    • 2022
  • This study reports a microfluidic approach to produce monodisperse hydrogel microparticles in a simple and highly efficient manner. Specifically, we produce double emulsion drops with a thin oil shell surrounding an aqueous prepolymer solution, which is solidified via UV-induced free radical polymerization. When they are dispersed in an aqueous solution, the oil shell is dewetted due to the absence of surfactants, resulting in production of highly uniform hydrogel microparticles (C.V.=1%). Results show that production of monodisperse hydrogel microparticles with controllable size and composition can be achieved with minimal use of oil unlike water-in-oil (w/o) single emulsion-based approach. Furthermore, in-depth study of flow patterns in microfluidic device using a phase diagram exhibits a crucial relationship among relative flow rates while providing windows of readily controllable parameters for reliable manufacturing of hydrogel microparticles.

Formation of Complex Between Polyelectrolytes and pH/Temperature Sensitive Copolymers (고분자전해질과 pH/온도감응성 고분자 사이의 복합체 형성에 관한 연구)

  • Yoo, Mi Kyong;Sung, Yong Kiel
    • Journal of the Korean Chemical Society
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    • v.42 no.1
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    • pp.84-91
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    • 1998
  • Random copolymers of N-isopropyl acrylamide (NIPAAm) and acrylic acid (AAc) which exhibit temperature- and pH-responsive behavior were synthesized by free-radical polymerization. The copolymers were characterized by means of FT-IR spectrometry and titration. The influence of polyelectrolyte on the lower critical solution temperature (LCST) of pH/temperature-sensitive polymers was investigated in the pH range of 2-12. The LCSTs of PNIPAAm/water in poly(NIPAAm-co-AAc) were determined by cloud-point measurements. A polyelectrolyte complex was prepared by mixing poly(NIPAAm-co-AAc) with poly(allylamine) (PAA) or poly(L-lysine) (PLL) solutions as anionic and cationic polyelectrolytes, respectively. Back titration was performed to determine the content of AAc and to study the effect of comonomer ionization on the LCST. The LCSTs of PNIPAAm/water in the copolymers were strongly affected by pH, presence of polyelectrolyte, AAc content, and charge density on the polymer. The polyelectrolyte complexes were formed at neutral condition. The influence of more hydrophobic PLL as polyelectrolyte on the cloud-point of PNIPAAm/water in the copolymer was stronger than that of poly(allylamine) (PAA).

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A Study on the Electron Beam Crosslinking of Acrylic Pressure Sensitive Adhesives for Polarizer Film (전자선 조사를 통한 편광필름용 아크릴계 고분자의 가교화 반응에 대한 연구)

  • Park, Jung-Jin;Choi, Hong-June;Ko, Hwan-Soon;Jeong, Eun-Hwan;Youk, Ji-Ho
    • Polymer(Korea)
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    • v.36 no.3
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    • pp.344-350
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    • 2012
  • New pressure sensitive adhesives (PSAs) for polarizer film were prepared by electron beam (e-beam) radiation to acrylic copolymers, and their adhesive properties were investigated. The acrylic copolymers were synthesized by free radical polymerization of $n$-butylacrylate (BA), 2-hydroxyethyl methacrylate (HEMA), and acrylic acid (AA). The acrylic copolymers were coated on PET release films to a thickness of 25 ${\mu}m$, laminated to polarizer films, and then radiated with e-beam at room temperature. Gel fractions of all the acrylic copolymers after e-beam radiation at 50 kGy were higher than 93%, and their crosslinking densities were increased with increasing the content of HEMA units. PSA prepared by e-beam radiation of acrylic copolymer synthesized with a feed ratio of BA/HEMA/AA = 89.5/10/0.5 (w/w/w) at a dose of 50 kGy exhibited the best adhesion performances in terms of peel strength, creep resistance, durability and reliability, and light leakage. It is expected that the preparation method of PSAs via e-beam irradiation will improve the producibility and workability of polarizer film for liquid crystal display.

The Effect of Ionic Group and MMA Contents on the Physical Properties of PU/PMMA Hybrids (PU/PMMA Hybrids의 물성에 대한 이온성기와 MMA함량의 영향)

  • Jeong, Chang Nam;Cho, Hang Kyu;Noh, Si Tae
    • Applied Chemistry for Engineering
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    • v.8 no.4
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    • pp.575-581
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    • 1997
  • UDs were synthesized from two different polyols(PTMG, PBEAG), ionic chain extender(DMPA), EDA with $H_{12}-MDI$. PU/PMMA hybrids were prepared with free radical polymerization of MMA monomer in MMA-swelled PUD. PUD particle size and film properties were investigated ionic content and polyol type. Mechanical and thermal properties of PU/PMMA hybrid film were studied in terms of PU's ionic content and the venation of PU/PMMA compositions. As DMPA content increased from 2wt% to 10wt% in PUD, particle size of PUD decreased. PUD's particle size with ester type polyol was found to be smaller then ether type polyol used. Phase separation between hard segment(HS) and soft segment(SS) with ionic contents in PU was shown by the thermal, mechanical property measurement. Although the composition of MMA was changed from 0 to 40 wt% in PU/PMMA hybrid, the particle size of the hybrid did not increase. Using the ester type polyol, tensile strength of hybrid was found to increase by 2wt% - 6wt% DPMA content, but as higher content the strength of hybrid decreased. Moreover with the ether type polyol, tensile strength of hybrid was observed to increase by 2wt% - 4wt% DMPA content, while decreasing at higher content. PU and PMMA polymer molecule being mixed in molecular level was confirmed from the pattern of $T_g$ in DSC thermogram.

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Surface Modification of Liposomes Using Comblike Copolymer for Enhancing Stability in Blood Circulation (혈류 내 안정성 향상을 위한 빗 모양 고분자로 개질된 리포솜)

  • Sin, Byeong-Cheol;Song, Chung-Gil;Hwang, Tae-Won;Seong, Ha-Su;Park, Eun-Seok
    • Journal of the Korean Chemical Society
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    • v.50 no.3
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    • pp.216-223
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    • 2006
  • To increase the stability of liposomes in blood circulation, surface modification of liposomes by incorporating a lipid-polymer derivative in the lipid bilayer or conjugating a hydrophilic polymer to the liposomal surface has been developed. In this study, the comblike copolymer, poly(HEMA-co-HPOEM), having multiple polyethyleneoxide side chains was prepared by free radical polymerization of hydroxyethylmethacrylate (HEMA) and hydroxypolyoxyethylenemethacrylate (HPOEM) as vinyl monomers. Poly(HEMA-co-HPOEM) was conjugated to the liposomal surface and the characteristics of the modified liposomes in serum were investigated. Conjugation of poly(HEMA-co-HPOEM) to liposomes increased the particle size of the liposomes by 30 nm and decreased the absolute value of zeta potential of the liposomes by shielding the negative charge of liposomal surface. Loading efficiency of model drug, doxorubicin, in liposomes was about 90% and the efficiency was not affected by conjugation of poly(HEMA-co-HPOEM) to liposomes. The particle size of poly(HEMA-co-HPOEM)-conjugated liposomes in serum did not changed and the protein adsorption was lower than that of control liposomes or liposomes containing polyethyleneoxide-lipid derivative (PEG-liposomes). These results suggest that poly(HEMA-co-HPOEM) is efficient for the stabilization of liposomes in blood circulation.

Synthesis and Optical Properties of Acrylic Copolymers Containing AlQ3 Pendant Group for Organic Light Emitting Diodes

  • Kim, Eun-Young;Myung, Sung-Hyun;Lee, Young-Hee;Kim, Han-Do
    • Clean Technology
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    • v.18 no.4
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    • pp.366-372
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    • 2012
  • Three acrylic copolymers containing tris(8-hydroxyquinoline) aluminum (AlQ3) pendant group (25 wt%), acrylateco-HEMA-$AlQ_3$ (25 wt%), were successfully synthesized by free radical polymerization from acrylates [methyl methacrylate (MMA), acrylonitrile (AN) or 2-hydroxyethyl methacrylate (HEMA)] with HEMA functionalized with AlQ3 pendant groups (HEMA-p-$AlQ_3$). The glass transition temperatures ($T_g$) of MMA-co-HEMA-p-$AlQ_3$ (copolymer 1), AN-co-HEMA-p-$AlQ_3$ (copolymer 2) and HEMA-co-HEMA-p-$AlQ_3$ (copolymer 3) were found to be 158, 150 and $126^{\circ}C$, respectively. They have good thermal stability: a very desirable feature for the stability of OLEDs. Their solubility, thermal properties, UV-visible absorption and photoluminescence behaviors were investigated. They were found to be soluble in various organic solvents such as tetrahydrofuran (THF), dimethylformamide (DMF), toluene and chloroform. It was also found that the UV-visible absorption and photoluminescence behaviors of these copolymers were similar to those of pristine $AlQ_3$. Green organic light-emitting diodes (OLEDs) have also been fabricated using these copolymers as light emission/electron transport components obtained easily by spin coating, and their current density voltage (J-V) curves were compared. The OLED device of the copolymer 3 had the lowest turn-on voltage of about 2 V compared to other copolymer types devices.