• 한국응용과학기술학회지
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• 제30권2호
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• pp.297-304
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• 2013

Free-radical copolymerization of glycidyl methacrylate(GMA) and N-phthalimidoethyl acrylate(NPEA) were carried out at $60^{\circ}C$ in dimethylformamide(DMF) solution in the presence of benzoylperoxide(BPO) at low conversion. The polymers were characterized by IR and $^1H$-NMR. The compositions of the copolymer was analyzed by ultra violet(UV/Vis) spectrophotometry. The reactivity ratios of the monomer was determined by the application of Fineman-Ross(FR) and Kelen-T$\ddot{u}$d$\ddot{o}$s(KT) methods. The monomer reactivity ratios of the system and Alfrey-Price's resonance effect(Q) and polar effect(e) value for NIEA were determined as follow. The reactivity ratios of the monomer obtained from FR and KT are found to be $r_1$=0.87, $r_2$=0.98 and $r_1$=0.88, $r_2$=0.99 respectively. The Q and e values of poly(GMA-co-NPEM) calculated from $r_1$ and $r_2$ was Q= 1.31, e=0.75 respectively.

• Macromolecular Research
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• 제17권12호
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• pp.1003-1009
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• 2009

Copolymers of N-vinylpyrrolidone (NVP) comonomer with styrene (St), hydroxypropyl methacrylate (HPMA) and carboxyphenyl maleimide (CPMI) were synthesized by free radical polymerization using 2,2'-azobisisobutyronitrile (AIBN) initiator in 1,4-dioxane solvent. The copolymers formed were characterized by FTIR, $^1H$ NMR and $^{13}C$ NMR techniques and their thermal properties were studied by DSC and TGA. Copolymer composition was determined by $^1H$ NMR and/or by elemental analysis and monomer reactivity ratios (MRR) were estimated by the linear methods of Kelen-Tudos (K-T) and extended Kelen-Tudos (EK-T) and the non-linear approach. Copolymers of St and HPMA with NVP formed blocks of one of the monomer units, whereas alternating copolymers were obtained in CPMI-NVP, depending upon the side chain substitution. The MRR values are discussed in terms of monomer structural properties such as electronegativity and electron delocalization. The sequence distribution of monomers in the copolymers was studied by statistical method based on the average reactivity ratios obtained by EK-T method.

• Nuclear Engineering and Technology
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• 제53권12호
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• pp.4130-4136
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• 2021

By polymerization of gadolinium methacrylate (Gd (MAA)₃), lead methacrylate (Pb(MAA)₂) and methyl methacrylate (MMA), Gd and Pb were chemically bonded into polymers. The X-ray shielding performance was evaluated by Monte Carlo simulation method, and the results showed that the more metal functional organic monomer, the better the shielding performance of terpolymers. When the X-ray energy is 65 keV, Gd (MAA)₃-containing polymers have better shielding performance than Pb(MAA)₂-containing polymers. Gd could compensate for the weak absorption region of Pb. Therefore, polymers containing both Gd and Pb enhanced shielding efficiency against X-ray in various low-energy ranges. For obtaining terpolymers with uniform monomer compositions, the relationship between the monomer composition of the terpolymers and the conversion level was optimized by calculating the reactivity ratios. The value of reactivity ratios of r (Gd (MAA)₃/Pb(MAA)₂), r (Pb(MAA)₂/Gd (MAA)₃), r (Gd (MAA)₃/MMA), r (MMA/Gd (MAA)₃), r (Pb(MAA)₂/MMA) and r (MMA/Pb(MAA)₂) was 0.483, 0.004, 0.338, 2.508, 0.255, 0.029. The terpolymers with uniform monomer composition could be obtained by controlling the monomer compositions or conversion levels. The results can provide new radiation protection materials and contribute to the improvement in nuclear safety.

• 폴리머
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• 제39권1호
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• pp.13-22
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• 2015

A new methacrylate copolymer that includes chalcone as a side group, poly(4-methacryloyloxyphenyl-4'-methoxystyryl ketone-co-styrene) was synthesized by free radical copolymerization. FTIR and $^1H$ NMR spectroscopic techniques were used to characterize the homopolymers and copolymers. The copolymerizations were carried out to high conversions. Copolymer compositions were established by $^1H$ NMR spectra analysis. The monomer reactivity ratios for copolymer system were determined by the linearized Kelen $T{\ddot{u}}d{\ddot{o}}s$, and Extended Kelen $T{\ddot{u}}d{\ddot{o}}s$ methods and a non-linear least squares method. The molecular weights and polydispersity index of copolymers were measured by using the gel permeation chromatography (GPC). The effect of copolymer compositions on their thermal behavior were studied by differential scanning calorimetry and thermogravimetric analysis methods. The optical properties of the resulting copolymer were also investigated.

• 폴리머
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• 제24권2호
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• pp.168-173
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• 2000

자유 라디칼 개시제인 2,2'-azobisisobutyronitrile (AIBN)을 사용하여 1,4-dioxane 용매하에서 N-isopropylacrylamide (NIPAAM)와 methyl methacrylate (MMA)를 공중합하였다. 온도에 따른 NIPAAM과 MMA의 반응성비를 알아보기 위해 각각 50, 60, 7$0^{\circ}C$에서 중합하여 전환율이 10 wt%이하가 되도록 반응을 정지시켰다. 단량체 반응성비는 Finemann-Ross법으로 구하였으며, 그 값은 5$0^{\circ}C$에서는 ${\gamma}$$_2$=0.259, ${\gamma}$$_2$=2.782, 6$0^{\circ}C$에서는 ${\gamma}$$_1$=0.271, ${\gamma}$$^2$=0.819, 그리고 7$0^{\circ}C$에서는 ${\gamma}$$_1$=0.286, ${\gamma}$$_2$=2.915로 나타나, 반응온도가 높아질수록 ${\gamma}$$_1$, ${\gamma}$$_2$ 값이 증가함을 알 수 있었다. 또한 반응온도와 반응성비와의 관계로부터 활성화에너지의 차를 구할 수 있었으며, 그 결과 반응성비는 온도 의존성이 있는 것으로 나타났다.

• 한국응용과학기술학회지
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• 제30권4호
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• pp.592-601
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• 2013

이 연구는 3-(1,8나프탈이미도)프로필메타아크릴레이트(NIPM)와 GMA공중합체의 합성과 물성에 관한 과제로서 나프탈이미드 발색단을 가진 공중합체의 조성, 모노머 반응성비, 공명효과(Q)와 극성효과 (e), 형광특성 등을 조사하였다. Azobisisobutyronitronitryl(AIBN) 개시제와 dimethylformamide(DMF) 용매를 $60^{\circ}C$에서 공중합하였다. Fineman-Ross(F-R)와 Kelen-$T\ddot{\bar{u}}d\ddot{\tilde{o}}s$(K-T)법으로 부터 단량체 반응성비를 구하였으며, $r_1$값이 $r_2$보다 크게 나타났다. NIPM이 공중합체내에서 GMA보다 더 많음을 알 수 있다. 380 nm에서 약한 분자형광띠와 460 nm에서 강한 중합체 엑시머 형광띠가 나타났다.

• 폴리머
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• 제38권4호
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• pp.535-543
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• 2014

이 논문은 napthalimidopropylacrylate(NIPA)와 glycidylmethacrylate(GMA) 공중합체의 합성과 물성에 관한 연구로서 공중합체의 조성, 단량체 반응성비, 공명효과(Q)와 극성효과(e), 나프탈렌발색단을 가진 물질의 형광특성 등을 조사하였다. Azobisisobutyronitronitryl(AIBN) 개시제와 dimethylformamide(DMF) 용매를 $60^{\circ}C$에서 공중합하였다. 단량체의 반응성비는 Fineman-Ross(F-R), Kelen-$T{\ddot{u}}d{\ddot{o}}s$(K-T) 법으로 단량체 반응성비를 구한바, $r_1$은 $r_2$보다 크게 나타났다. NIPA이 GMA보다 공중합의 형성이 더 많음을 알 수 있다. 단량체 반응성비의 곱($r_1{\cdot}r_2$)이 1보다 적어서 불규칙한 교대공중합체가 형성되었고 다른 단량체끼리 결합하게 된 교호공중합체를 형성된 것으로 간주된다. 380 nm에서 약한 분자 형광띠와 460 nm에서 강한 중합체 엑시머 형광띠가 나타났다. NIPA 단량체의 형광수명은 실온에서 UV 355 nm 파장에서 형광붕괴커브를 나타냈으며 $5.1449{\times}10^{-7}s$로 나타났다. GMA 공단량체를 아크릴계에 공중합시켜 우수한 내열성 열경화성 접착제나 코팅제에 응용될 것으로 사료된다.

• 대한화학회지
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• 제13권4호
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• pp.373-377
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• 1969

In order to determine the monomer reactivity ratio in copolymerization of acrolein, the copolymerization of acrolein with styrene, methyl methacrylate and vinyl acetate respectively was studied. The Q and e value of acrolein in each copolymerization were also calculated from those of monomer reactivity ratios, but the calculated values were slightly different from each other. The Q and e of acrolein for the system of acrolein-styrene copolymerization were Q = O.64 and e = O.62 respectively. Relations among the Q and e value, the composition and structure of copolymers and the mean sequence length in copolymerization were also discussed for acrolein copolymers.

• 한국응용과학기술학회지
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• 제26권2호
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• pp.205-212
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• 2009

Solution copolymerization of Styrene(St.) with 2-Hydroxypropylacrylate(2-HPA) was carried out with Benzoylperoxide(BPO) as an initiator in toluene at $80^{\circ}C$ in a batch reactor. Reaction volume and reaction time were 0.3 liters, 8 hours respectively. The time to reach steady state was about the six time. The monomer reactivity ratios, $r_1$(St.) and $r_2$(2-HPA) were determined by both the Kelen-Tudos method and the Fineman-Ross method ; $r_1$(St.)=0.376(0.330), $r_2$(2-HPA)=0.408(0.778). The activation energy of thermal decomposition was in the range of $33{\sim}55kcal/mol$.

• 대한화학회지
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• 제15권5호
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• pp.281-284
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• 1971

Copolymerization of glycidyl methacrylate(GMA) with methyl acrylate(MA) and the reaction of the copoly mer with primary amines were investigated. The monomer reactivity ratios were determined by Mayo-Lewis intersecting method. $r_1=0.22{\pm}0.03(GMA),\;r_2=0.50{\pm}0.07(MA)$. GMA and MA copolymerized to afford the polymer having good alternate arrangements of the units of the monomers.