• Title/Summary/Keyword: Ziegler-Natta

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Effect of ${\gamma}$-Ray Irradiation on Surface Oxidation of Ultra High Molecular Weight Polyethylene/Zirconia Composite Prepared by in situ Ziegler-Natta Polymerization

  • Kwak, Soon-Jong;Noh, Dong-Il;Chun, Heung-Jae;Lim, Youn-Mook;Nho, Young-Chang;Jang, Ju-Woong;Shim, Young-Bock
    • Macromolecular Research
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    • v.17 no.8
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    • pp.603-608
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    • 2009
  • Novel ultra-high molecular weight polyethylene (UHMWPE)/zirconia composites were previously prepared by the in situ polymerization of ethylene using a Ti-based Ziegler-Natta catalyst supported on to the surface of zirconia, as a bearing material for artificial joints. Tribological tests revealed that a uniform dispersion of zirconia in UHMWPE markedly increased the wear resistance. The effects of zirconia content on the oxidation behavior of the ${\gamma}$-ray-treated UHMWPE/zirconia composite surfaces were examined. The oxidation index that estimates the oxidation degree as the content of total carbonyl compounds was monitored using Fourier transform infrared spectroscopy-attenuated total reflectance. The changes in the surface composition due to the oxidation were confirmed by electron spectroscopy for chemical analysis. The extent of oxidation decreased with increasing zirconia content, which was attributed to the increased crystallinity as well as the decreased polymer portion of the UHMWPE/zirconia composites.

Linear Low Density Polyethylene Preparation by Titanium-Based Ziegler-Natta Catalysts (티탄이 기본인 Ziegler-Natta 촉매에 의한 선형저밀도폴리에틸렌의 제조)

  • Dong-Ho Lee;Kyung-Eun Min;Cha-Ung Kim
    • Journal of the Korean Chemical Society
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    • v.31 no.1
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    • pp.110-117
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    • 1987
  • For the preparation of linear low density polyethylene (LLDPE), the copolymerization of ethylene and 1-butene was carried out with various catalysts of titanium alkoxidealkylaluminum compound in slurry phase. The effects of catalyst components, aging time, concentration of catalyst components, polymerization time and temperature on the catalytic activity and copolymer composition were examined. The properties of copolymer obtained were also considered with the correlation to the 1-butene contents. It has been found that the titanium tetra-n-butoxide-diethylaluminum chloride catalyst system was the most suitable for the production of LLDPE with higher catalytic activity, more 1-butene content and less soluble parts. The density, glass transition temperature, melting point and heat of fusion of copolymer were decreased with increasing 1-butene contents.

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The Effect of Comonomer Type and Content on the Properties of Ziegler-Natta Bimodal High-Density Polyethylene (공단량체의 종류 및 조성이 지글러-나타 중합된 이중 분자량 분포 고밀도 폴리에틸렌의 물성에 미치는 영향)

  • Meng, Weijuan;Li, Hongbo;Li, Jianwei;Chen, Biaohua
    • Journal of the Korean Chemical Society
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    • v.55 no.4
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    • pp.673-679
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    • 2011
  • Bimodal high-density polyethylenes with different comonomer type and content were synthesized by polymerization of ethylene using Ziegler-Natta catalyst. Their structure and properties were studied using GPC, NMR, DSC and tensile test. It was found that ethylene/1-hexene copolymer exhibits higher tensile strength and elongation at break than that of ethylene/1-butylene copolymer with similar comonomer content. The molecular weight decreases as the comonomer content of the polymer increases. Short chain branching affects the crystallinity and thus the morphology and consequently the mechanical properties of the corresponding bimodal high-density polyethylenes. After SSA treated, the multiple endothermic peaks were observed. Multiple endothermic peaks are mainly attributed to the heterogeneity of ethylene sequence length and lamellar thickness. The difference of broadness index indicates that SCB distribution of polyethylene containing higher comonomer content has improved uniformity.

Morphological Properties of Binary Blends of Polyolefins Synthesized by Metallocene and Ziegler-Natta Catalysts (Ziegler-Natta와 메탈로센 촉매로 합성된 폴리올레핀 2원 블렌드의 상 형태학)

  • Kwag, Hanjin;Kim, Hak Lim;Choe, Soonja
    • Applied Chemistry for Engineering
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    • v.10 no.6
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    • pp.944-948
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    • 1999
  • The morphological properties of four binary blends of polyethylene synthesized by metallocene catalyst(MCPE) and four polyolefins prepared by Ziegler-Natta catalyst have been investigated to interpret the effect of micro-molecular structure on the phase morphology and interfacial behavior; four binary blend systems studied are high density polyethylene(HDPE)-metallocene polyethylene (MCPE), polypropylene(PP)-MCPE, poly(propylene-co-ethylene) (CoPP)-MCPE, and poly(propylene-co-ethylene-co-1-butylene) (TerPP)-MCPE, and they are all phase separated. The HDPE-MCPE blend shows evenly growing homogeneous HDPE domain on the continuous MCPE phase, on the other hand, the rest of three blends show complex heterogeneous phase behavior. The PP-MCPE blend shows that PP and MCPE and completely phase separated and phase inversion takes place at 50% MCPE. The CoPP-MCPE and TerPP-MCPE show enhanced interface due to the same micro-molecular structure of ethylene, and phase inversion takes place at 40% MCPE. In particular, TerPP-MCPE blend shows improved phase morphology between interfaces, and this may be arisen from the comonomer contents in TerPP, which are 1-butene and ethylene having the same chemical structure as that of MCPE. The enhancement of the phase morphology in the TerPP-MCPE blend is correlated with the mechanical and morphological properties. Thus, although the four blend systems are phase separated, the phase morphology suggests that the order of interfacial adhesion strength be HDPE-MCPE > TerPP-MCPE > CoPP-MCPE > PP-MCPE and that micro-molecular structure between constituents be one of major factors giving enhanced interfacial adhesion.

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Degradation of cis-Polyisoprene in Supercritical Tetrahydrofuran (Tetrahydrofuran의 초임계 상에서 cis-Polyisoprene의 분해)

  • Kim, H.J.;Hong, I.K.
    • Elastomers and Composites
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    • v.32 no.5
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    • pp.302-308
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    • 1997
  • Over 1953/54 Karl Ziegler and Giulio Natta independently discovered new types of catalyst. Thus it was able to produce synthetic cis-polyisoprene rubber which has same properties like natural rubber, since then the amount of consumption was increased rapidly. The problem of disposing of used rubbers has become acute in recent years. cis-Polyisoprene was degraded in supercritical tetrahydrofuran and degree of degradation and product were observed by GPC, FT-IR, GC-MS analyses. As a result, degradation of cis-polyisoprene had small dependency upon the operating pressure, and was inhibited in concentration increase. And cis-polyisoprene was degraded into narrow molecular weight distribution oligomer in 3 hours, and more than 10 organic compounds were produced.

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The Color and Spectroscopic Properties of Polyacetylene Derivatives(Ⅵ): Synthesis and Properties of Poly (2-ethynyl-N-methylpyridinium iodide ) and Poly (2- ethyny1-N-methylpyridinium tetraphenylborate)

  • 이원철;제갈영순;진성호;임용진
    • Proceedings of the Korean Society of Dyers and Finishers Conference
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    • 2003.04a
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    • pp.197-202
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    • 2003
  • 아세틸렌 화합물의 삼중결합은 2개의 $\pi$-결합을 가지고 있는 전자풍부 화학종으로서 다양한 촉매 system에 의해서 비교적 쉽게 부가중합반응이 진행되며 이를 통하여 공액구조 고분자를 쉽게 제조할 수 있다. 가장 간단한 삼중결합 화합물인 아세틸렌은 다양한 촉매 system에 의해서 쉽게 부가중합반응이 진행되어 분말상의 폴리아세틸렌이 합성되었으며 1974년 일본의 Shirakawa 등은 Ziegler-Natta 촉매의 일종인 Ti(OC$_4$H$_{9}$)$_4$-Al(C$_2$H$_{5}$)$_3$(Al/Ti = 3-4) 촉매 system을 사용하여 실험한 결과 은빛의 필름형 폴리아세틸렌의 합성에 성공하였다. (중략)

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Chemical Compositional Distribution of Ethylene-1-Butene Copolymer Prepared with Heterogeneous Ziegler-Natta Catalyst: TREF and Crystaf Analysis

  • Ko, Young-Soo;Jeon, Jong-Ki;Yim, Jin-Heong;Park, Young-Kwon
    • Macromolecular Research
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    • v.17 no.5
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    • pp.296-300
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    • 2009
  • Ethylene-1-butene copolymers were prepared with $SiO_2$-supported $TiCl_4$ catalyst by changing of 1-butene/ethylene molar ratio in feed, and the resulting copolymers were analyzed using temperature rising elution fractionation (TREF) and crystallization fractionation (Crystaf) methods to investigated the influence of $C_4/C_2$ molar ratio in feed on chemical compositional distribution and other parameters such as molecular weight and its distribution. TREF analysis showed that the copolymers had a broad and bimodal chemical compositional distribution (CCD) regardless of the content of 1-butene in the copolymer. The chemical composition was in the range of 5 to 55 branches per 1,000 carbons for all copolymers prepared in the study. Furthermore, the broader CCD was revealed for the copolymers having the higher content of 1-butene. Crystaf analysis did not showed a bimodal CCD for the copolymers having the 1-butene content of less than 5.1 wt%. The lower crytalline part having 1-butene content in Crystaf analysis was less than of TREF analysis.

Crystallization Characteristics of Metallocene Low Density Polyethylene/Low Density Polyethylene Blends (메탈로센 선형 저밀도 폴리에틸렌/선형 저밀도 폴리에틸렌 블렌드의 결정화 거동)

  • 김경룡;한정우;강호종
    • Polymer(Korea)
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    • v.25 no.6
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    • pp.840-847
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    • 2001
  • The crystallization characteristics of metallocene linear low density polyethylene (m-LLDPE)/linear low density polyethylene (LLDPE) blends were investigated. The effect of blending on the induction time for crystallization, spherulites growth rate, and maximum size of spherulites was mainly considered in this study. The formation of separate crystal which is well known crystallization behavior in LLDPE/LDPE blend was not found in m-LLDPE/LLDPE blends. The blending m-LLDPE to LLDPE caused the dramatic decrease in the induction time of m-LLDPE/LLDPE blends but it seems that the blend composition shows less effect on the induction time. Lower branching number in m-LLDPE resulted in the increasing of spherulites growth rate and the maximum size of spherulites is depend upon both the induction time and spherulites growth rate of LLDPE component affected by m-LLDPE.

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Polymerization of fibrous and high molecular weight polyethylene using MgCl2/SBA-16/TiCl4

  • Panpoom, Salinla;Klinsrisuk, Sujitra;Martwiset, Surangkhana;Poonsawat, Choosak
    • Particle and aerosol research
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    • v.11 no.4
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    • pp.107-113
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    • 2015
  • SBA-16 (Santa Barbara Amorphous) was synthesized over supported $TiCl_4/MgCl_2$. Due to its high surface area and excellent morphological performance, it was expected to form the bi-supported catalytic system and be used for ethylene polymerization. Polymerization of ethylene was carried out at atmospheric pressure using hexane as solvent and triethylaluminium as cocatalyst. ICP, FTIR, DSC, TG-DTA were used to characterize polyethylene and catalyst product. Optimum conditions for ethylene polymerization were found to be 100 mL hexane, Al/Ti molar ratio of 160 and 1 h polymerization at $60^{\circ}C$. The activity of 396.76 kg PE/mol Ti.h.atm was achieved. Melting point of the obtained polymer was in the range of $132-135^{\circ}C$ and the highest degree of crystallization was 46%.

Novel Cationic Group 4 Metal Alkyl Complexes for Olefin Polymerizations (올레핀중합용 첨단 양이온형 제4족 유기금속 착물)

  • Kim, Il
    • Polymer Science and Technology
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    • v.5 no.3
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    • pp.236-253
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    • 1994
  • 양이온형 $d^0\;Cp_2M(R)(L)^+$ 착물과 무염기 $Cp_2M(R)^+$ 착물은 $Cp_2M(R)_2$화합물로부터 쉽게 합성할 수 있다. 이들 친전자성 착물에서는 여러가지 리간드 교환반응, 삽입반응, ${\beta}$-H 제거반응 및 ${\sigma}$-결합 복분해반응이 일어날 수 있다. 일반적으로 $Cp2M(R)(L)^+$ 착물은 불포화도와 전하가 크기때문에 중성의 $Cp_2M(R)(X)$$Cp_2M(R)_2$보다 반응성이 크며 $d^0\;{Cp_2}^*M(R)^+$ (M=제 3족과 란탄계) 착물과 여러가지 반응에서 유사한 거동을 보인다. $Cp_2MX_2$를 기초로하여 합성된 Ziegler-Natta 촉매에 의한 올레핀 중합에서 활성점이 $Cp_2M(R)^+$ 양이온이라는 여러가지 직접적인 증거가 발표되었다. 분리가능한 $Cp_2M(R)(L)^+$ 착물은 올레핀중합에서 높은 활성을 보이며, 유기합성의 관점에서 흥미있는 C-C 재조합반응과 같은 다른 여러가지 반응이 일어날 수 있는 기회를 제공한다.

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