• 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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• 제28권12호
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• pp.2471-2476
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• 2007

A series of titanium complexes containing terdentate β-ketoiminate ligands were found to be efficient for the ring-opening polymerization of ε-caprolactone (ε-CL), producing poly(ε-caprolactone) (PCL) with bimodal distribution. Steric factors imposed by methyl substituents on the back bone of the alkoxy group affected significantly the polymerization rate and physical properties of the resulting PCL. Intra- and intermolecular transesterifications rather than disproportional rearrangements were responsible for the bimodal behavior and for the change in the molecular weight (Mw). Dilution with toluene reduced yield, and lowered polydispersity (PDI) and Mw of PCL, while the catalytic activities of the dimeric complex, [Ti(Oi-Pr)2(N-alkoxy-β- ketoiminate)]2 and Ti(Oi-Pr)4 were not sensitive to the added solvent. The dimeric complex showed living character, while other catalysts suffered from chain termination reactions.

• 폴리머
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• 제30권4호
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• pp.357-361
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• 2006

생체 내에서 생성되는 알파 리포산은 산화방지, 혈당량 조절뿐만 아니라 식욕 억제, 비만 억제 효과 등을 가지고 있다. 약물로도 이용되고 있는 이 물질은 두 개의 황을 함유하고 있는 오각형 고리구조를 가지고 있어, 열과 자외선에 의해서 쉽게 개환되고 나아가 고분자로 중합될 수 있어서 약물로서 투여했을 경우 생체 이용률이 낮아지는 문제가 보고되어 있다. 본 연구는 개환에 따른 고분자화를 위한 다양한 조건을 조사하였다. 리포산은 녹는점이 지나야만 개환이 발생하였지만 그 이상의 온도에서는 온도의존성이 없었다. $70^{\circ}C$에서 개환율은 시간에 비례하였고 농도에 반비례하였다. 1시간 동안, $70^{\circ}C$ 아세트산에서 자외선과 함께 개환된 경우 개환율은 가장 높은 70% 였다. 이렇게 개환된 알파 리포산들은 대부분이 이황 고분자로 변했고, 개환율이 커질수록 고분자의 분자량 도 증가하였다.

• 폴리머
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• 제33권5호
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• pp.458-462
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• 2009

본 연구에서는 순차적 음이온 및 개환중합반응을 통해 ABC 형태의 폴리스티렌-폴리에틸렌옥사이드-폴리락티드 블록공중합체를 성공적으로 합성하였다. 우선, 첫번째 블록인 폴리스티렌을 합성하기 위해서, 사이클로헥산 용매에서 스티렌/이차-부틸리튬을 각각 단량체/개시제로 사용하여 음이온중합(anionic polymerization)을 수행하였고, 이후 고분자 말단을 수산기로 전환시키기 위해, 에틸렌옥사이드를 첨가하였다. 다음 단계로 포타슘 나프탈레나이드(potassium naphthalenide)를 이용하여 폴리스티렌 말단 수산기의 수소를 제거하여, 거대개시제인 PS-$O^-K^+$를 제조하였다. 준비된 거대 개시제에 정량된 에틸렌옥사이드를 첨가하여, 음이온중합을 수행하였다. 폴리락티드 블록을 도입시키는 개환중합의 경우, THF 용매에서 트리에틸알루미늄(triethylaluminum)/피리딘(pyridine)시스템을 이용하여 PS-b-PEO-$AlEt_2$ 형태의 거대개시제를 형성한 후, $90^{\circ}C$에서 중합을 수행하였다. 합성된 블록공중합체를 수소핵자기공명법 및 겔침투크로마토그래피 방법을 통해 조사한 결과, 잘 정의된 분자량 및 낮은 분자량 분포를 나타냄을 확인할 수 있었다.

• 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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• 제14권2호
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• pp.205-208
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• 2006

A polymeric film of a biodegradable poly(1,5-dioxepan-2-one) (PDXO) was formed on a gold surface by a combination of the formation of self-assembled monolayers (SAMs) presenting hydroxyl groups and the surface-initiated, ring-opening polymerization (SI-ROP) of 1,5-dioxepan-2-one (DXO). The SI-ROP of DXO was achieved by heating a mixture of $Sn(Oct)_2$, DXO, and the SAM-coated substrate in anhydrous toluene at $55^{\circ}C$. The resulting PDXO film was quite uniform. The PDXO film was characterized by polarized infrared external reflectance spectroscopy, X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, atomic force microscopy, ellipsometry, and contact angle goniometry.

• 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.

• 통합자연과학논문집
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• 제2권2호
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• pp.78-81
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• 2009

In recent years, organometallic polymer containing silane and silole unit has been a topic of interest because of the wide range of optical, electrical and luminescent properties. In previous work, we synthesized functionalsilanebridged[1]ferrocenophane from the reaction of dimethyldichlorosilane[Me2SiCl2] and diphenyldichlorosilane[Ph2SiCl2] and dichloromethylvinylsilane[C3H6SiCl2] with ferrocene$[Fe({\eta}-C5H4)2]$ and n-BuLi. In this work, we have synthesized Poly(ferrocenylsilane) via the Thermal Ring-Opening Polymerization(ROP). characteristics of the poly(ferrocenylsilane) were investigated by gel permeation chromatography(GPC), 1H- and 13C-NMR spectroscopy.

• 청정기술
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• 제12권2호
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• pp.62-66
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• 2006

다양한 폴리디메틸실록산계 공중합체를 안정화제로 이용하여 초임계 이산화탄소 내에서의 개환중합을 통해 PLLA를 제조하였다. 초임계 개환중합에 사용된 폴리디메틸실록산 공중합체는 폴리디메틸실록산 거대개시제를 사용하여 그룹전이중합법(GTP법)을 이용하여 제조하였다. $\small{L}$-락타이드의 초임계 현탁중합을 통해 수미크론크기의 입자가 형성되었음을 전자 주사 현미경을 통해 확인하였고, 또한 겔 투과 크로마토 그라피 분석을 통해 상당히 좁은 분자량 분포의 PLLA가 제조되었음을 확인하였다.

• Composites Research
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• 제32권6호
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• pp.375-381
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• 2019

Multiwalled carbon nanotubes (MWCNTs) are covalently functionalized with isocyanates by directly reacting commercial hydroxyl functionalized MWCNTs with excess 4,4'-methylenebis (phenyl isocyanate) (MDI) and hexamethylene diiosocyanate (HDI). HDI-modified MWCNTs results in a higher surface isocyanate density than MDI-modified MWCNTs. Anionic ring-opening polymerization of ε-caprolactam is conducted using a sodium caprolactam initiator in combination with a di-functional hexamethylene-1,6-dicarbamoylcaprolactam activator in the presence of isocyanate functionalized MWCNTs. This polymerization proceeds in a highly efficient manner at relatively low reaction temperature (150℃) and short reaction times (10 min). During the polymerization, the isocyanate functionalized MWCNTs act not only as reinforcing fillers but also as second activators. Nanocomposites with HDI modified MWCNTs exhibit higher reinforcement and faster isothermal crystallization than MDI modified MWCNTs. The results show that PA6 chains grow more effectively from HDI modified MWCNT surface than from MDI modified MWCNT surface, resulting in stronger interaction between PA6 and MWCNTs.