Pd (II)-catalyzed vinyl addition polymerization of novel functionalized norbornene bearing dimethyl carboxylate groups

Liu, Binyuan,Li, Yang,Shin, Boo-Gyo,Yoon, Do Yeung,Kim, IL,Zhang, Li,Yan, Weidong Wiley Subscription Services, Inc., A Wiley Company 2007 Journal of polymer science Part A, Polymer chemist Vol.45 No.15

<P>Three novel functionalized polynorbornenes (PNB) with pendant dimethyl carboxylate group (carboxylates—acetate, propionate, and butyrate) are synthesized as a vinyl-type with a palladium (II) catalyst in high yield. The effects of size of substitutents, molar ratio of monomer to catalyst, solvent polarity, reaction time, and temperature on the polymerization of exo-norbornene dimethyl propionate were systematically investigated. The low molar ratio and temperature, as well as high polarity of solvent, and long reaction time, are favorable for the enhancement of the monomer conversion, especially, the solvent have an obvious effect on the catalyst activity. The resulting poly(cis-norbornene-exo-2,3-dimethyl carboxylates) (PNB-dimethyl carboxylates) show good solubility in common organic solvent and high thermal stability up to 360 °C. The glass transition temperature was detected by DMA at 331, 324, and 318 °C for acetate, propionate, and butyrate, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3391–3399, 2007</P> <B>Graphic Abstract</B> <P>Three novel functionalized PNB-2,3-dimethyl carboxylates (carboxylates—acetate, propionate, butyrate) are synthesized as a vinyl-type with a palladium (II) catalyst in high yield. The resulting PNB-dimethyl carboxylates show good solubility in common organic and high thermal stability up to 360 °C. The glass translation temperature was determined by DMA at 331, 324, and 318 °C for PNB-dimethyl acetate, PNB-dimethyl propionate, and PNB-dimethyl, respectively.</P><P> <img src='wiley_img/0887624X-2007-45-15-POLA22091-gra001.gif' alt='wiley_img/0887624X-2007-45-15-POLA22091-gra001'> </P>

Ring-Opening Polymerization of $\varepsilon$-Caprolactone and Cyclohexene Oxide Initiated by Aluminum $\beta$-Ketoamino Complexes: Steric and Electronic Effect of 3-Position Substituents of the Ligands

Liu, Binyuan,Li, Haiqing,Ha, Chang-Sik,Kim, Il,Yan, Weidong The Polymer Society of Korea 2008 Macromolecular Research Vol.16 No.5

A series of aluminum complexes supported by $\beta$-ketoamino, ligand-bearing, 3-position substituents $LAlEt_2$ ($L=CH_3C(O)C(Cl)=C(CH_3)NAr\;(L_1)$, $L=CH_3C(O)C(H)=C(CH_3)NAr\;(L_2)$, $L=CH_3C(O)C(Ph)=C(CH_3)NAr\;(L_3)$, and $L=CH_3C(O)C(Me)=C(CH_3)NAr\;(L_4)$, $Ar=2,6-^iPr_2C6H_3$) were synthesized in situ and employed in the ring-opening polymerization (ROP) of $\varepsilon$-caprolactone ($\varepsilon$-CL) and cyclohexene oxide (CHO). The 3-position substituents on the $\beta$-ketoamino ligand backbone of the aluminum complexes influenced the catalyst activity remarkably for both ROP of $\varepsilon$-CL and CHO. Aluminum $\beta$-ketoamino complexes displayed different catalytic behavior in ROP of $\varepsilon$-CL and CHO. The order of the catalytic activity of $LAlEt_2$ was $L_1AlEt_2$>$L_2AlEt_2$>$L_3AlEt_2$>$L_4AlEt_2$ for ROP of $\varepsilon$-CL, being opposite to the electron-donating ability of the 3-position substituents on the $\beta$-ketoamino ligand, while the order of the catalytic activity for ROP of CHO was $L_1AlEt_2$>$L_3AlEt_2$>$L_4AlEt_2$>$L_2AlEt_2$. The effects of reaction temperature and time on the ROP were also investigated for both $\varepsilon$-CL and CHO.

중국 허난(河南)성 문화창의산업의 경제적 파급효과 분석

장빈원(Zhang Binyuan),가장장(Jia Tingting),배기형(Ki-Hyung Bae) 한국콘텐츠학회 2021 한국콘텐츠학회논문지 Vol.21 No.7

본 연구는 허난성 산업연관표를 활용하여 중국 허난성 문화창의산업에 대한 경제적 파급효과의 분석 결과를 바탕으로 문화창의산업의 미래지향적인 시사점을 제시하는 데 목적을 두고 있다. 본 연구를 위해 중국 허난성 통계국의 2017년 산업연관표의 42개 산업 중 문화 · 체육 · 오락, 연구 및 시험 발전, 종합 기술 서비스, 정보 전송 · 컴퓨터 서비스 및 소프트웨어, 교육 등 5개 부문을 문화창의산업으로 분류하였다. 분석 결과는 다음과 같다. 허난성 문화창의산업의 총생산유발액은 48,848 십억 위안이며, 특히 허난성 문화창의산업 산업의 생산유발계수는 2.72809, 2.23909 (열 합계, 행 합계), 감응도계수 0.26325, 영향력계수 0.87535, 소득유발계수 0.55211, 생산세유발계수 0.09291 등을 보여주고 있다. 중국 허난성 문화창의산업은 발전할 잠재력이 충분히 있기 때문에 정부의 정책 지원 필요하고 법적 규정과 시장관리에 대한 감독이 요구되고 문화창의산업의 혁신력을 높이고 문화창의산업+X 융합 모델 개발도 필요하다. The purpose of this research is to analyze the Spill-over economic effect of the cultural and creative industries(CCI) in Henan Province, China. The research object is the CCI of Henan Province, which is mainly based on five sectors out of 42 industries in the industrial association table of the Statistical Bureau of Henan Province, China in 2017 (culture, sports; recreation and research sector; experimental development and integrated technical services sector; information transmission, computer services and software sector; education sector, etc), and is analyzed through secondary integration and redefinition of the CCI of Henan Province. Through the analysis of Henan Province Industry Association Table, this paper provides some enlightenment to the future direction of the cultural and creative industries. The main analysis results are as follows. The total production inducement of the CCI in Henan province is 48,848 billion yuan, and in particular, the production inducement coefficient of the industry in Henan province is 2.72809, 2.23909 (total of columns and rows), Index of the power of dispersion is 0.26325, and the index of the sensitivity of dispersion is 0.87535. Income induction coefficient is 0.55211, production tax induction coefficient is 0.09291. Because CCI of Henan Province has full development potential, the government needs to provide active support and policy support, in addition to the need for legal provisions and supervision of market management. In order to improve the innovative development of the CCI, it is necessary to develop a new model of CCI+X.

중국 소비자 지각된 가치가 고궁박물관 문화 창의 제품의 제품 태도와 구매 의도에 미치는 영향

장빈원(Zhang Binyuan),방기위(Pang Qiwei),위영매(Wei Yingmei),배기형(Ki-Hyung Bae) 한국콘텐츠학회 2021 한국콘텐츠학회논문지 Vol.21 No.8

본 연구의 목적은 고궁박물관 문화 창의 제품의 발전 측면에서 소비자 지각된 가치가 제품 태도와 소비자구매 의도에 미치는 영향을 검증하여 연구결과를 기초로 제품의 측면에서 발전전략을 제공하는데 있다. 이를 위해 선행연구를 바탕으로 실증분석을 실시하였다. 설문 조사는 최근에 구매한 경험이 있는 소비자들을 대상으로 305개의 유효한 설문지를 수집하였으며 분석결과는 다음과 같다. 소비자의 지각된 가치 3가지 변수가 제품 태도에 모두 유의한 정(+)의 영향을 미치며, 지각된 문화교육 가치가 소비자의 구매의도에 유의한 영향을 미치지 않지만, 다른 변수들이 소비자의 구매 의도에 모두 유의한 정(+)의 영향을 미치는 것으로 나타났다. 또한, 소비자의 제품 태도가 구매 의도에 긍정적인 영향을 미치는 것으로 검증되었으며, 소비자의 지각된 가치중의 지각된 기능 가치, 지각된 오락 가치와 구매 의도 사이에 제품 태도의 부분 매개 효과가 있는 것으로 나타났다. 연구결과에 따라 문화 창의 제품은 문화적 정체성을 유지하면서 유쾌함과 편안함을 최대한 끌어올리는 방법을 고려하여 합리적인 가격과 일상적으로 사용하는 기능적 가치도 풍부해야 한다. 또한 고궁 문화창의 제품에 담긴 문화 지식에 대해서는 해석과 설명을 제공할 필요가 있다. The Palace Museum Cultural Creative Products on Attitude and Purchasing Intention. Online surveys were conducted on consumers who had consumed Cultural and Creative Products of the Palace Museum in the past. There were 305 valid questionnaires empirical survey was analyzed. The results of the study are as follows. First, it was found that all three variables of Consumer Perceived Value had a significant positive effect on product Attitude. Second, among the three variables of Consumer Perceived Value, the Cultural Educational Value did not significantly affect the onsumer urchasing ntention, but other variables had a significant positive effect on the Consumer Purchasing Intention. Third, it was verified that Attitude has a positive effect on Purchasing Intention. Fourth, it was found that there was a partial mediating effect of the Attitude between the Perceived Value and the Consumer Purchasing Intention. According to the research results, while maintaining the cultural identity of cultural and creative products, it is necessary to adopt reasonable methods to maximize the sense of enjoyment and comfort, enriching the daily use functions and rationalizing the price standards.

The Synthesis of Norbornene Derivatives and Polymerization

윤도영,Binyuan Liu 한국고분자학회 2002 한국고분자학회 학술대회 연구논문 초록집 Vol.2002 No.10

Coupling reaction of carbon dioxide and epoxides efficiently catalyzed by one-component aluminum–salen complex under solvent-free conditions

Dawei Tian,Binyuan Liu,Li Zhang,Xiaoyang Wang,Wei Zhang,Lina Han,Dae Won Park 한국공업화학회 2012 Journal of Industrial and Engineering Chemistry Vol.18 No.4

Four novel bifunctional aluminum–salen complexes (2a, 2b, 2c, and 2d) containing both Lewis acidic metal center and Lewis base quaternary phosphonium salt sites within one molecule and an aluminum–salen complex with a neutral tert-butyl group (2f) for comparison were synthesized and characterized by UV–vis, IR, 1H, 13C, 27Al NMR spectroscopy and Elemental analysis (EA). Their catalytic efficiencies as single-component catalysts toward the coupling reaction of carbon dioxide and propylene oxide were evaluated. These complexes exhibit catalytic activity in the order 2d > 2a > 2b > 2c 2f. 27Al NMR spectra reveal the existence of five- and six-coordinated metal centers in the aluminum–salen complexes bearing a quaternary phosphonium salt group, whereas only five-coordinate aluminum species were found in the aluminum–salen complex with a neutral tert-butyl group. This indicates the importance of the six-coordinate aluminum center in enhancing the catalytic activity as well as an intramolecular cooperative effect in bifunctional aluminum–salen complexes 2a–d. The effects of reaction variables on the catalytic performance were investigated in detail. These new catalysts are highly stable to moisture and air and robust to impurities in the coupling reaction.

Synthesis and Structure-Property Relationships of Poly(norbornene dicarboxylic acid dialkyl esters) and Poly(norbornene dimethyl carboxylates)

신부교,조태연,강지훈,Binyuan Liu,윤도영 한국고분자학회 2004 한국고분자학회 학술대회 연구논문 초록집 Vol.29 No.2

Controllable Synthesis of Stereoregular Polyesters by Organocatalytic Alternating Copolymerizations of Cyclohexene Oxide and Norbornene Anhydrides

Han, Bing,Zhang, Li,Liu, Binyuan,Dong, Xiaofang,Kim, Il,Duan, Zhongyu,Theato, Patrick American Chemical Society 2015 Macromolecules Vol.48 No.11

<P>A facile strategy has been demonstrated for the selective synthesis of highly stereoregular polyesters with <I>cis</I>-2,3-(<I>exo</I>,<I> exo</I>) or <I>trans</I>-2,3-(<I>exo</I>,<I> endo</I>) repeating units by the organocatalysts mediated alternating copolymerization of cyclohexene oxide and norbornene anhydride (NA) stereoisomers. The geometrical structure of polyester can be tuned simply by modulating the type of NA isomers (<I>endo</I>- or <I>exo</I>-NA), monomer feed ratio, and reaction temperature. The <I>cis</I>- (>99%) and <I>trans</I>-polyesters (>99%) exhibit high glass transition temperature up to 129.8 and 115.9 °C, respectively. The resulting polyesters provide a versatile platform to incorporate various functional groups through the robust thiol–ene reaction of the pendant norbornenyl groups.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/mamobx/2015/mamobx.2015.48.issue-11/acs.macromol.5b00555/production/images/medium/ma-2015-00555x_0010.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ma5b00555'>ACS Electronic Supporting Info</A></P>

Copolymerizations of Ethylene with 1-Hexene over MgCl2/SiO2 Bi-Supported Titanium Catalysts: Effect of SiO2 on Active Site Distribution

Hegang Ren,김일,Min Yang,Yujin Liu,Binyuan Liu,Jiayan Qu,Yanji Wang 한국고분자학회 2012 Macromolecular Research Vol.20 No.2

Addition Polymerization of 5-Ethylidene-2-norbornene by Cationic Palladium Cationic Complex and Subsequent Derivatization

Luhai Wang,김일,Xiaoya Wang,Min Yang,Yige Wang,Li Li,Binyuan Liu 한국고분자학회 2011 Macromolecular Research Vol.19 No.10

Poly(5-ethylidene-2-norbornene) (PENB) was synthesized via a vinylic pathway using a cationic palladium-based catalyst, displaying high activity up to 1.06×10^6 g-PENB/mol Pd. The effects of the monomer to catalyst ratio, temperature, reaction time, and concentration on the polymerization were investigated systematically. The control tests and spectroscopic analyses of the PENB indicate that 5-ethylidene-2-norbornene is polymerized via an addition polymerization using endocyclic double bonds. The post-modification was also performed using a free radical graft polymerization. The resulting PENB copolymers were characterized by IR, ^1H NMR, and GPC analyses.