• Macromolecular Research
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• 제9권4호
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• pp.206-209
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• 2001

One of the approaches to obtain functional polymer is polymerization of a monomer having two functional groups. Although polymerization of a monomer having two different types of functional group is general, the author has been interested in the polymerization of a monomer having two similar types of functional group. This work shows the preparation and selective polymerization of 4-methylene-2-styryl-1,3-dioxolane having two similar reactive double bonds via cationic polymerization at ambient temperature. Cationic ring-opening polymerization of 4-methylene-2-styryl-1,3-dioxolane using benzylsulfonium salt as a photo-initiator quantitatively afforded high molecular weight of poly(keto-ether).

• Bulletin of the Korean Chemical Society
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• 제20권6호
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• pp.663-666
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• 1999

The 4-methylene-1,3-dioxolane(4-MDO) derivatives with dimethoxyphenyl group on the 2-position of 1,3-dioxolane ring, 2-(x,y-dimethoxyphenyl)-4-MDO derivatives (x,y=2,3(1b), 2,4(2b), 2,5(3b) and 3,4(4b)) were prepared by acelalizationof the corresponding benzaldehyde with 3-chloro-1,2-propanediol, followed by dehydrochlorination. 2-(Dimethoxy)phenyl-4-MDO derivatives underwent polymerization wiht ring opening as will as cyclization reaction to afford a mixture of the ring-opened polymer and 3(2H)-dihydrofuranone derivative with boron trifluoride as a cationic catalyst. Both the methylene group and 1,3-dioxolane ring were participated in the reaction with cationic catalyst. The key intermediate of the polymerization is a benzyl cation generated by ring opening, and the cyclization reaction proceed via proton addition to oxygen atom of 1,3-dioxolane ring.

• Macromolecular Research
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• 제17권9호
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• pp.651-657
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• 2009

This study examined the optimum compositions of binder, photo-acid generator (PAG) and sensitizer for the cationic ring opening polymerization of 1,3-bis[2-(3-{7-oxabicyclo-[4.1.0]heptyl})]-tetramethyldisiloxane in the presence of polydimethylsiloxane with four epoxide moieties as a co-monomer. When diffractive efficiency (DE) values were compared quantitatively to analyze the effect of the binder on holographic photopolymerization, DE was affected by the viscosity of the binders and miscibility with the monomer mixture. Extremely low DE values were observed when the immiscible dimethyl silicone was used as a binder. Therefore, methylphenyl silicone, which is miscible with the monomer mixture, was used as the binder for further studies. The optimal conditions were a binder viscosity between 250 to 390 cP, and contents of the binder, PAG, and sensitizer were 75-125 wt%, > 6 wt% and 0.05 wt% to the total monomer mixture, respectively.

• Bulletin of the Korean Chemical Society
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• 제20권12호
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• pp.1433-1436
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• 1999

The 2-(2,4-dimethoxyphenyl)-4-MDO (2) underwent polymerization with ring opening as well as cyclization reaction in the presence of various cationic catalysts such as boron trifluoride, trifluoromethanesulfonic acid, p-toluenesulfonic acid, hydrochloric acid and trifluoroacetic acid. They afforded a mixture of the ring-opened poly(keto ether) and 3(2H)-dihydrofuranone derivative. Both the methylene group and oxygen atom of 1,3-dioxolane ring were participated in the reaction with cationic catalyst. The contents of the polymer and cyclization product were variable according to the acid strength of the cationic catalysts.

• 한국고분자학회:학술대회논문집
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• 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
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• pp.199-199
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• 2006

Microwave-irradiation has become a common heat source in organic chemistry in the last decade. In recent years, polymer chemists also discovered the advances of microwave heating that include fast and efficient heating as well as the homogeneous heat profile and the easy access to pressurized reaction conditions. In this contribution, we report our investigations on the cationic ring-opening polymerization of 2-oxazolines that lead to a tremendous acceleration from several days to several minutes polymerization time. In addition, the optimized microwave-assisted polymerization procedure was applied for the preparation of libraries of diblock and triblock copolymers that were used for the determination of structure-property relationships in poly(2-oxazoline)s.

• 한국군사과학기술학회지
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• 제12권2호
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• pp.228-235
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• 2009

We synthesized glycidyl azide monomer(GAM) as a monomer for polymerization of glycidy azide polymer(GAP) which is a promising energetic prepolymer for a plastic-bonded explosive. Using quantitative real-tim in-situ infrared(in-situ IR) spectroscopy, kinetic study on the cationic ring opening polymerization of GAM was carried out. The reaction rate was obtained from monitoring the change of ether C-O stretching band($1050cm^{-1}$) in series IR spectra. The reaction was in accordance with the first-order reaction law for each of reaction temperature at 100/1 mole ratio of [GAM]/[$BF_3*etherate$]. In the ring opening polymerization of GAM, with ratio of [GAM]/[$BF_3*etherate$] to equal 100/1 at various temperature, the activation parameters obtained from the evaluation of kinetic data were ${\Delta}H^*$=14.34kcal/mol, ${\Delta}S^*=-12.31cal/mol{\cdot}K$ and $E_a$=14.89kcal/mol.

• 한국추진공학회:학술대회논문집
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• 한국추진공학회 2006년도 제26회 춘계학술대회논문집
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• pp.229-232
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• 2006

Tetrahydrofuran(THF)과 Ethylene oxide(EO) 또는 EO를 단량체로 하여 양이온 개환중합을 이용한 새로운 합성방법으로 random 또는 tri-block HTPE(Hydroxyl-terminated polyether)를 합성할 수 있었다. 합성된 random과 tri-block HTPE를 IPDI/N-100혼합 디이소시아네이트 경화제와 촉매로 TPB(triphenylbismuth)를 사용하여 폴리우레탄을 제조하였으며, 혼합 이소시아네이트 화합물의 비율에 따른 폴리우레탄의 기계적 특성을 연구하였다. 그리고 폴리 우레탄 추진제 바인더 제조를 위한 prepolymer인 합성된 HTPE의 최적 경화 조건을 찾기 위해 HTPE의 후처리 과정, 우레탄 합성시 사용되는 촉매의 양 등의 영향에 대해 알아보았다.

• 한국추진공학회:학술대회논문집
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• 한국추진공학회 2008년도 제31회 추계학술대회논문집
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• pp.231-236
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• 2008

양이온 개환중합법을 이용하여 Epichlorohydrin(ECH)과 Tetrahydrofuran(THF)을 공중합 하였다. 중합은 1,4-Butandiol 존재 하에 $BF_3THF$를 촉매로 사용하여 잘 제어된 Copolyetherdiol을 합성하였다. 분자량은 [monomer]/[diol]비를 조절하였고, 공중합체 조성은 ECH와 THF의 투입몰비를 변화하여 조절하였다. 합성된 Copolyetherdiol의 Chlorine기는$S_N2$반응을 이용하여 Azide기로 치환하였다. 합성된 고분자를 프리폴리머로 사용하여 경화제인 N-100/IPDI와 경화촉매인 TPB/MA 혼합촉매를 이용하여 Polyurethane을 합성하여 경화거동과 기계적 특성은 비교 분석하였다.

• Bulletin of the Korean Chemical Society
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• 제20권10호
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• pp.1195-1199
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• 1999

2-(2,4,5-Trimethoxyphenyl)-4-methylene-1,3-dioxolane (1b), 2-(2,4,6-trimethoxyphenyl)-4-methylene-1,3-di-oxolane (2b), and 2-(3,4,5-trimethoxyphenyl)-4-methylene-1,3-dioxolane (3b) were prepared and polymerized with boron trifluoride. Boron trifluoride catalyzed reaction proceeded via mainly ring-opening polymerization and cyclization reaction to yield poly(keto ether) and 3(2H)-dihydrofuranone. The yields of polymer and cyclized product exhibited a dependency on the position of the methoxy substituents in the benzene ring of 2-phenyl-4-methylene-1,3-dioxolane derivatives. Electrophilic attack of methylene or oxygen atom on 4-meth-ylene-1,3-dioxolane ring were suggested for the polymerization and cyclization.

• 한국군사과학기술학회지
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• 제8권2호
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• pp.67-76
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• 2005

We synthesized an energetic prepolymer(glycidyl dinitro propyl formal, GDNPF) for plastic-bonded explosive and measured its thermodynamic parameters. Glycidyl dinitro propyl formal(GDNPF) as an energetic monomer was epoxidized from allyl-2,2-dinitro propyl formal which is reacted with dinitro propyl alcohol and excess allyl alcohol, and then energetic polymer of GDNPF was polymerized by cationic ring opening polymerization. Thermodynamic parameters were obtained from the ceiling temperature($T_c$) values of 1 mole monomer at reaction temperature. We varied feed rate of monomer, concentration of initiator and monomer to control molecular weight and polydispersity of prepolymer (GDNPF). The activated monomer polymerization has been executed with precisely controlled feed of GDNPF monomer to reactor in the complex state catalyst generated by $BF_3{\cdot}(C_3H_5)_2$ and 1,4-butanediol in $C_2H_4Cl_2$. Number average molecular weight(Mn), polydispersity(Pd), hydroxy number and glass transition temperature($T_g$) of prepolymer(GDNPF) were $2,500{\sim}3,000,\;1.2{\sim}1,3,\;0.6{\sim}0.8eq/kg\;and\;-20{\sim}-25^{\circ}C$ respectively.