• Macromolecular Research
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• 제10권2호
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• pp.97-102
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• 2002

The mixtures of non-conjugated dienes, 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene (MHD), were successfully synthesized by the reaction of isoprene with ethylene using Fe(III)-based catalyst in toluene. The conversion was over 96 mol% on the basis of the initial amount of isoprene used. The production yield for MHD was nearly 50 mol%, the other was polyisoprene. The mixtures were successfully copolymerized with ethylene by using zirconium-based metallocenes. The products were characterized by the combinations of gas chromatography, high temperature gel permeation chromatography, $^1$H NMR, $^{13}$ C NMR, high temperature $^1$H NMR, UV/visible spectroscopy, and differential scanning calorimetry. It was found that 5-methyl-1,4-hexadiene was active enough to be incorporated into the copolymer chain but the corresponding isomeric material,4-methyl-1,4-hexadiene, was inactive in metallocene-catalyzed copolymerizations. Specifically, in the zirconocene-catalyzed copolymerizations of ethylene with MHD, ansa-structure catalysts seem to be more efficient than non-bridged type zirconocene. The degree of incorporation of MHD in the resulting copolymers was able to be controlled by the amount of non-conjugated dienes used initially.

• 공업화학
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• 제29권4호
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• pp.461-467
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• 2018

본 연구에서는 $(n-BuCp)_2ZrCl_2$를 $SiO_2/MgCl_2$ 이원 지지체에 담지시켰다. 촉매를 담지하기 전, $SiO_2/MgCl_2$ 이원 지지체를 3종의 알킬알루미늄 화합물, 트리메틸알루미늄, 트리에틸알루미늄 또는 에틸알루미늄 세스퀴클로라이드로 표면처리 하였다. 합성된 표면 처리된 $SiO_2/MgCl_2$에 담지된 메탈로센 촉매로 에틸렌 및 1-헥센의 공중합을 하였다. 촉매 특성 및 성능을 BET, XPS 분석, ICP-AES 분석 및 FE-SEM을 통해 비교 분석하였다. 생성된 공중합체를 DSC 분석, GPC 분석, 13C-NMR 분석 및 FE-SEM을 통해 비교 분석하였다. 합성된 $SiO_2/MgCl_2$ 담지된 메탈로센 촉매의 분석은 이들 촉매의 Zr 함량이 $SiO_2$에 담지된 촉매에 비해 상대적으로 낮다는 것을 보여 주었다. 이것은 재결정된 $MgCl_2$ 및 알킬알루미늄의 존재로 인한 $SiO_2$의 표면적 감소에 기인할 수 있다. 또한, $SiO_2/MgCl_2$ 담지된 메탈로센 촉매는 $SiO_2$에 담지된 메탈로센 촉매보다 활성이 높았으며 이 중 EASC-표면 처리 이원 지지체에 담지된 메탈로센촉매가 1.9 kg PE/($mmol-Zr^*hr$)의 가장 높은 활성을 보였다. 이것은 EASC가 강한 루이스 산으로 작용하기 때문이다. 또한, 사용된 알킬알루미늄의 리간드가 클수록 생성된 중합체의 입자 표면이 더 거칠었다.

• 폴리머
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• 제24권4호
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• pp.445-452
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• 2000

다양한 종류의 메탈로센 촉매와 공촉매인 개질-MAO (MMAO)을 이용한 에틸렌 (E)과 노르보르넨 (N)의 공중합에서 중합조건이 촉매 활성 및 공중합체의 구조와 성질 등에 미치는 영향을 조사하였다. 즉 $C_2$-대칭구조를 가지는 rac-Et(Ind)$_2$ZrC $l_2$, $M_2$Si(Ind)$_2$ZrC $l_2$, M $e_2$Si-(Cp)$_2$ZrC $l_2$ 및 $C_{s}$-대칭구조를 가지는 iPr(FluCp)ZrC $l_2$, 그리고 constrained geometry catalyst (CGC)와 이중다리 (di-bridged) 지르코노센 둥의 다양한 메탈로센 촉매를 사용하여 [N]/[E] 공급비에 따른 촉매 활성, 공중합체 (COC)의 열적 성질 및 N 함량을 조사하였다. rac-Et(Ind)$_2$ZrC $l_2$를 촉매로 사용한 경우에 공촉매의 몰비, 중합 온도 및 공촉매 종류 등의 중합조건을 조사한 결과 [Al]/[Zr]=3000, 4$0^{\circ}C$, MMAO 공촉매 등이 적합하였다. [N]/[E] 공급비가 증가됨에 따라 COC내의 N 함량이 증가하는 일반적인 경향을 보였으나, 촉매 활성은 사용된 메탈로센 촉매의 구조에 따라 달랐다. 즉 [N]/[E]가 증가할수록 $C_2$-대칭구조의 촉매 활성은 감소하였으나 $C_{s}$-대칭구조의 경우에는 증가하였다. 촉매활성과 N함량 등을 고려해 보면 rac-Et(Ind)$_2$ZrC $l_2$/MMAO계에서 비교적 높은 촉매 활성과 COC의 $T_{g}$제어가 용이한 결과를 얻을 수 있었다. 촉매종류에 따른 단량체의 반응성비를 Helen-Tudos 방법으로 구하였다.하였다.

• 폴리머
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• 제25권4호
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• pp.468-475
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• 2001

$rac-Et(Ind)_2ZrCl_2,\;rac-Me_2Si(Ind)_2ZrCl_2,\;rac-Me_2Si(Cp)_2ZrCl_2,\;(n-BuCp)_2ZrCl_2$ 등의 메탈로센 촉매와 공촉매인 개질 메틸알루민옥산(MMAO)을 이용한 에틸렌과 노르보르넨의 공중합에서 1-헥센(H), 1-옥텐 및 1-데센 등과 같은 ${\alpha}$-올레핀을 제3단량체로 첨가할 때, 중합조건, 촉매의 구조 및 ${\alpha}$-올레핀의 종류와 첨가량이 촉매 활성, 생성 중합체의 열적 성질 및 조성 등에 미치는 영량을 조사하였다. ${\alpha}$-올레핀의 첨가량에 따른 촉매 활성 및 중합체의 열적 성질의 변화는 촉매구조 뿐만 아니라 ${\alpha}$-올레핀의 구조에도 의존하였다. $rac-Et(Ind)_2ZrCl_2/MMAO$계에서 촉매 활성이 높았고 중합체의 $T_g$ 제어가 용이하였으며, 제3단량체로 H를 첨가한 경우에 가장 높은 촉매활성의 증가를 확인하였다.

• 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.

• 한국고분자학회:학술대회논문집
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• 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
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• pp.156-157
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• 2006

Quasi-living polymerization conditions for the copolymerization of ethylene and functionalized norbornenes can be achieved by using an initiator system comprising $[N-(2,6-diisopropylphenyl)-2-(2,6-diisopropylphenylimino)-propanamidato-{\kappa}^2N,O]Ni({\Box}^1-CH_2Ph)(PMe_3)\;and\;Ni(COD)_2$. It is possible with this polymerization system to obtain block-copolymer and tapered structures. The latter form microdomains similar to those of standard block co-polymers. The mechanism of the reaction will also be discussed.

• 한국고분자학회:학술대회논문집
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• 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
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• pp.221-221
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• 2006

The stereochemical control in polypropylenes and styrene-ethylene copolymers based on homogeneous single-site polymerization catalysts has received great attention since the stereocpecificity is one of the key factors in tailoring the polymer properties. Thus, we have developed new tactics for isospecificity in propylene polymerization with the unbridged metallocenebased systems and syndiospecific styrene-styrene sequence in styrene-ethylene copolymerization with the group 4 metallocene system. Brief details of the synthesis, structures and the polymerization behavior of a set of new metallocene catalysts will be presented.

• Macromolecular Research
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• 제12권1호
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• pp.100-106
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• 2004

We have prepared the polymethylene-bridged, dinuciear, half-sandwich constrained geometry catalysts (CGC)［Zr(η$\^$5/:η$^1$-C$\_$9/H$\_$5/SiMe$_2$NCMe$_3$)］$_2$［(CH$_2$)$\_$n/］［n=6(9), n=12(10)］by treating 2 equivalents of ZrCl$_4$with the corresponding tetralithium salts of the ligands in toluene. $^1$H and $\^$13/C NMR spectra of the synthesized complexes provide firm evidence for the anticipated dinuciear structure. In $^1$H NMR spectra, two singlets representing the methyl group protons bonded at the Si atom of the CGC are present at 0.88 and 0.64 ppm, which are considerably downfield positions relative to the shifts of 0.02 and 0.05 ppm of the corresponding ligands. To investigate the catalytic behavior of the prepared dinuciear catalysts, we conducted copolymerizations of ethylene and styrene in the presence of MMAO. The prime observation is that the two dinuclear CGCs 9 and 10 are not efficient for copo-lymerization, which definitely distinguishes them from the corresponding titanium-based dinuclear CGC. These species are active catalysts, however, for ethylene homopolymerization; the activity of catalyst 10, which contains a 12-methylene bridge, is larger than that of 9 (6-methylene bridge), which indicates that the presence of the longer bridge between the two active sites contributes more effectively to facilitate the polymerization activity of the dinuciear CGC. The activities increase as the polymerization temperature increases from 40 to 70$^{\circ}C$. On the other hand, the molecular weights of the polyethylenes are reduced when the polymerization temperature is increased. We observe that dinuciear metallocenes having different-length bridges give different polymerization results, which reconfirms the significant role that the nature of the bridging ligand has in controlling the polymerization properties of dinuclear catalysts.

• 통합자연과학논문집
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• 제13권1호
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• pp.13-18
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• 2020

This study used cerium iron hydroxide nanoparticle with HEMA (2-hydroxyethyl methacrylate), the cross-linker EGDMA (ethylene glycol dimethacrylate), NVP (N-vinyl-2-pyrrolidone) and the initiator AIBN (azobisisobutyronitrile) for copolymerization. Also, the physical properties of the prepared lenses were compared, and their applicability as polymers for ophthalmic materials was experimented. The results of the measurement showed that the UV blocking rate and the wettability increased with the cerium iron hydroxide nanoparticles addition ratio, and the refractive index and water content were not affected. Thus, the produced copolymer is expected to be useful as a functional contact lens material while satisfying the basic physical properties of the hydrogel contact lens.

• 방사선산업학회지
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• 제6권1호
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• pp.49-54
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• 2012

Various anion exchange membranes were prepared by radiation graft copolymerization of vinylbenzyl chloride onto fluorinated films and subsequent quaternization with various tertiary amines such as trimethylamine, N,N-dimethylbuthylamine, N,N-dimethylaniline, and N-methylpiperidine. The quaternizations of the anion exchange membranes were confirmed by measuring of the ion exchange capacities of the membranes. The mechanical properties and the water uptakes were also measured. The elongation at break was found to be largely dependent on the fluorinated film, the quateranry ammonium, and the degree of grafting. The results indicate that the poly (ethylene-alt-tetrafluoroethylene) with quaternized trimethylamine moiety exhibits higher flexible property compared to the other prepared anion exchange membranes.