• Macromolecular Research
• /
• 제15권1호
• /
• pp.17-21
• /
• 2007

A series of new, vinyl sulfone-containing monomers was prepared by p-aminophenyl vinyl sulfone (1) with various acid chlorides such as adipoly chloride, terephthaloyl chloride and isophthaloyl chloride. Finally, tertiary amine-containing poly(amide-sulfone)s were prepared by the Michael-type addition polymerization using N,N-dimethylethylenediamine (DMEDA), p-phenylenediamine and piperazin. To evaluate the relevant properties for permselective membranes and enzyme substrate, various physical properties such as molecular weight, solubility, quaternization behavior and thermal properties were examined.

• Bulletin of the Korean Chemical Society
• /
• 제32권6호
• /
• pp.1884-1890
• /
• 2011

A series of Ni(II) and Pd(II) complexes bearing N4-type tetradentate ligands, [Ni($X^1X^2$-6-$Me_2bpb$) 1] and [Pd($X^1X^2$-6-$Me_2bpb$) 2]; 6-$Me_2bpb$ = N,N'-(o-phenylene)bis(6-methylpyridine-2-carboxamidate), $X^1$ = Cl, H, or $CH_3$, $X^2$ = $NO_2$, Cl, F, H, $CH_3$, or $OCH_3$) were designed, synthesized, and characterized to investigate electronic and steric effects of ligand on the norbornene polymerization catalysts. Using modified methylaluminoxanes as an activator, the complexes exhibited high catalytic activities for the polymerization of norbornene and the nickel complexes exhibited better catalytic activity the palladium complexes. Ni complex 1a with $NO_2$ group on the benzene ring showed the highest catalytic activity of $4.9{\times}10^6$ g of PNBEs/$mol_{Ni}{\cdot}h$ and molecular weight of $15.28{\times}10^5$ g/mol with PDI < 2.30. Complexes with electron-withdrawing groups are more thermally stable (> 100 $^{\circ}C$), and tend to afford higher polymerization productivities than the ones having electron-donating groups. Amorphous polynorbornenes were obtained with good solubility in halogenated aromatic solvents. A vinyl addition mechanism has been proposed for the catalytic polymerization.

• 한국재료학회지
• /
• 제30권6호
• /
• pp.273-278
• /
• 2020

This research is conducted to analyze the compatibility of used monomers and produce the high functional hydrogel ophthalmic polymer containing silane and nanoparticles. VTMS (vinyltrimethoxysilane), TAVS [Triacetoxy(vinyl)silane] and cobalt oxide nanoparticles are used as additives for the basic combination of SilM (silicone monomer), MMA (methyl methacrylate) and MA (methyl acrylate). Also, the materials are copolymerized with EGDMA (ethylene glycol dimethacrylate) as cross-linking agent, AIBN (thermal polymerization initiator) as the initiator. It is judged that the lenses of all combinations are optically excellent and thus have good compatibility. Measurement of the optical and physical characteristics of the manufactured hydrophilic ophthalmic polymer are different in each case. Especially for TAVS, the addition of cobalt oxide nanoparticles increases the oxygen permeability. These materials are considered to create synergy, so they can be used in functional hydrogel ophthalmic lenses.

• Bulletin of the Korean Chemical Society
• /
• 제33권12호
• /
• pp.4131-4136
• /
• 2012

Several palladium complexes containing ${\beta}$-ketoiminate and ${\beta}$-diketiminate ligands successfully produced poly(DCPD) possibly via vinyl addition. It was found that catalysts with ${\beta}$-diketiminate ligands containing bulkier aryl substituents showed the highest activity in the presence of MAO as a cocatalyst. Purity of DCPD is quite essential for the higher activity and small amount of organic solvent such as $CH_2Cl_2$ and toluene is required to reduce the viscosity of the reactant mixture for the higher activity. $^1H$ NMR spectra of produced polymers with N,N-dimethylanilinium tetra(pentafluorophenyl)borate (N,N-DAPFAr"$_4$) show that 5,6-double bond of DCPD is removed with 2,3-double bond remaining. Produced poly(DCPD) with MAO cocatalyst is quite rigid and insoluble in common organic solvents but rather brittle.

• 폴리머
• /
• 제27권5호
• /
• pp.429-435
• /
• 2003

양이온η$^3$-알릴 팔라듐 촉매를 사용하여 환상형 올레핀 단량체인 노보넨 (NB)과 5-비닐-2-노보넨(VNB)을 조성별로 비닐 부가 공중합하였다. 공중합체는 고수율과 고분자량 (M$_{w}$ > 760000)으로 얻을 수 있었다. VNB 함량이 많아질수록 공중합체의 분자량과 수득율은 감소하였으며, 첨가한 공단량체의 양과 공중합한 후 함유된 단량체의 양이 비례함을 FT-IR 분광분석으로 확인하였다. $^1$H-NMR 분석 결과 VNB는 exo, endo 이성체 모두 중합에 참여하는 것을 알 수 있었다. NB-VNB 공중합체의 분해 개시 온도는 약 300 $^{\circ}C$이었고, 열안정성은 VNB 함량과 관계없이 유사한 거동을 나타내었다. 합성된 NB-VNB 공중합체의 곁사슬 비닐기는 m-CPBA를 이용하여 에폭시화 하였고, 또한 9-BBN을 이용하여 수산화기를 도입하였다. 조성별 공중합체에 각각의 치환기가 도입된 것은 FT-IR, $^1$H-NMR 분석으로 확인하였다..

• Macromolecular Research
• /
• 제17권4호
• /
• pp.250-258
• /
• 2009

One-step seeded polymerization was used to prepare $7{\sim}10{\mu}m$ of crosslinked monodisperse spheres with four crosslinking agents using $4.68{\mu}m$ poly(methyl methacrylate)(PMMA) seed particles in aqueous-alcoholic media in the absence of the swelling process. The crosslinking agents used were ethylene glycol dimethacrylate(EGDMA), allyl methacrylate(AMA), 1,6-hexanediol diacrylate(HDDA) and trimethylolpropane trimethacrylate(TMPTMA). The effects of the type and concentration of the crosslinking agents on the swelling, pore size, thermal property of the networks and morphology of the particles were studied. The chemical structures and concentrations of the crosslinking agents affected both the swelling ratio and the porosity of the networks. In addition, the chemistry of the reactive vinyl group and chain length of the crosslinking agents affected the stability of the monodisperse particles of the ultimate morphology.

• 한국섬유공학회:학술대회논문집
• /
• 한국섬유공학회 2003년도 가을 학술발표회 논문집
• /
• pp.177-178
• /
• 2003

Many researchers have made efforts to control the stereoregularity in radical polymerization of vinyl monomers because the physical and chemical properties of the polymer are significantly affected by the stereostructure.[1]-[4] In general, monomer design, reaction conditions(e.g. solvent, temperature, and monomer concentration), and additives can alter the stereochemistry of the radical polymerization of acrylic monomer. (omitted)

• 폴리머
• /
• 제28권3호
• /
• pp.245-252
• /
• 2004

5-헥실-2-노보넨 (HNB)과 5-메틸에스터-2-노보넨 (MES-NB)을 양이온 ${\eta}^3$-알릴 팔라듐 촉매인 [(${\eta}^3$-allyl) palladium(tricyclohexylphosphine) trifluoroacetate]와 리튬계 조촉매 [lithium tetrakis(pentafluorophenyl( borate${\cdor}$2.5etherate]를 사용하여 비닐 부가형의 폴리노보넨 공중합체를 합성하였다. 에스터기를 과량 함유한 폴리노보넨을 제조하기 위한 최적 중합 조건을 조사하기 위하여 여러가지 중합조건에 따른 분자량변화와 수율의 변화를 알아보았다. 팔라듐 촉매의 함량이 많을수록 수득율은 증가하는 한편, 분자량은 감소하였으며, 리튬조촉매의 함량은 많을수록 분자량과 수득율이 동시에 증가하였다. 사슬이동체를 이용하여 분자량을 조절할 수 있었고, 사슬이동제의 길이가 긴 1-데센과 1-옥텐이 1-헥센보다 분자량을 더 감소시키는 역할을 하였다. 한편 사슬이동제의 양은 수율에 큰 영향을 미치지 않았다. HNB/MES-NB(투입비 40/60 mol%)의 공종합체의 $^1$H-NMR 과 GPC 분석으로부터, 실제 에스터 함유량으 약 25mol%인 고분자량 (M$_{w}$ : 270,000)의 폴리노보넨 공중합체가 얻어짐을 알 수 있었다.

• 한국고분자학회:학술대회논문집
• /
• 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
• /
• pp.296-296
• /
• 2006

Highly temperature stable mesoporous materials have excellent properties and potential applications. Here we show a novel poly(vinyl)silazane-block-polystyrene diblock copolymer, which was synthesized by controlled/living free radical polymerization with reversible addition fragmentation chain transfer (RAFT) route. The obtained diblock copolymer occurs the phaseseparation on the nanoscale to form ordered nanostructure, which is converted to mesoprorous ceramic after heating at 800oC. This route demonstrates the preparation of highly temperature stable mesoporous silicon carbon nitrides (SiCN) ceramic film directed from highly cross-linking poly(vinyl)silazane blocks with high ceramic yield, which is different from previous pathway.

• 공업화학
• /
• 제27권3호
• /
• pp.313-318
• /
• 2016

본 연구에서는 무정형 실리카의 세공 내를 아미노실란인 N-[(3-trimethoxysilyl)propyl]ethylenediamine (2NS)를 이용하여 표면 기능화한 후 표면 기능화된 실리카에 후전이 금속 촉매인 $(DME)NiBr_2$와 $PdCl_2$(COD)를 담지하여 노보넨 중합을 실시하였다. 중합 온도와 중합 시간, Al/Ni 몰비, 조촉매 종류를 변화시켜 중합 특성에 미치는 영향을 조사하였다. 담지되지 않은 촉매($(DME)NiBr_2$, $PdCl_2$(COD))로 노보넨 중합을 수행하였을 경우 중합반응은 일어나지 않았다. 그러나 조촉매로 MAO를 이용하여 중합한 경우 $SiO_2$/2NS/Ni 촉매는 중합 온도가 증가할수록 활성은 증가하였고 폴리노보넨(polynorbornene, PNB)의 분자량은 급격하게 감소하였다. $SiO_2$/2NS/Pd 촉매는 온도가 증가할수록 활성과 PNB의 분자량 모두 감소하는 경향을 보였다. $SiO_2$/2NS/Ni 촉매는 $SiO_2$/2NS/Pd 촉매보다 높은 온도에서 안정함을 확인하였다. 또한 두 촉매 모두 중합 시간이 길어질수록 노보넨의 전환율은 증가하였다. Al/Ni 몰비가 1000 : 1일 때 가장 높은 활성(15.3 kg-PNB/(${\mu}mol-Ni^*hr$))을 보이는 반면 가장 낮은 분자량($M_n$ = 124,000 g/mol)의 PNB를 합성하였다. 또한 조촉매로 Borate/TEAL을 이용하여 중합한 경우 $SiO_2$/2NS/Ni 촉매는 중합 온도가 증가할수록 활성과 분자량이 모두 감소하였다.