金子林
长期从事有机化学的教学和研究工作,主要研究领域是环境友好催化与精细化学品清洁生产工艺。具体的研究方向有:液/液两相催化、CO化学与均相催化、非离子表面活性剂与环氧乙烷化学。
个性化签名
- 姓名:金子林
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学术头衔:
博士生导师
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学科领域:
有机化学
- 研究兴趣:长期从事有机化学的教学和研究工作,主要研究领域是环境友好催化与精细化学品清洁生产工艺。具体的研究方向有:液/液两相催化、CO化学与均相催化、非离子表面活性剂与环氧乙烷化学。
主要学历及工作经历:1957年毕业于大连工学院化工系并留校任教。1963-1967年东德德累斯顿工大(TU Dresden)研究生,1981年获德国亚琛工大TH Aachen 博士学位。同年回国。历任大连理工大学化工学院副院长、化工研究所所长等职。现为该校有机化学教授,应用化学博士点博导。
主要学术及社会兼职:精细化工国家重点实验室学术委员会委员,《石油化工》杂志编委,中国洗涤剂协会科技委员会委员,德国化学家协会表面活性剂专业委员会成员。
研究领域(研究课题):长期从事有机化学的教学和研究工作,主要研究领域是“环境友好催化与精细化学品清洁生产工艺”。具体的研究方向有:“液/液两相催化”、“CO化学与均相催化”、“非离子表面活性剂与环氧乙烷化学”。
具体研究课题有:国家自然科学基金:温控相转移摧化芳香硝基物CO还原;非离子水溶性膦配体的临界温度及其在均相催化中的应用研究。教育部博士点基金:芳香胺类的环境友好合成技术研究。德国DFG资助的中德合作研究项目:用于温控两相催化的含乙氧基链芳膦配体的合成研究。其它研究课题:油醇的化工新利用--油醇的温控相转移羰基合成;高聚物的液/液两相加氢反应研究;新型液/液两相催化体系的研究。
科研成果及所受奖励:近年的主要学术创新是提出“温控相转移催化”概念,这一概念已作为词条被2001年国际出版的催化百科全书“Catalysis from A to Z”(Wiley-VCH,Weinheim)收编,并被国内外广泛引用和评述,先后在国际专著“Aqueous phase Organometallic Catalysis”(Eds:B.Cornils,W.A.Herrmann)(1998)和国际丛书“Current Topis in Catalysis”(Research Trends,2001)中以专章和专论介绍,这一获得国家自然科学基金九.五重大项目的资助研究课题正在不断向纵深发展。目前,在做深化和创新以温控膦配体为基础的新型液/液两相催化体系研究的同时,继续扩展“温控相转移催化”的反应类型并力争推向工业应用。最新提出的“温控相分离催化”概念是本研究组在液/液两相催化方面的又一研究成果。
近十年中,作为第一获奖人,获得以下省部级学术奖项:1.环境友好液/液两相催化新过程―温控相转移催化 辽宁省自然科学奖二等奖; 2001 2.温控相转移催化及其应用技术 教育部科技进步(甲类)二等奖 1998 3.氯卞羰化一步合成苯乙酸 教育部科技进步一等奖 4.壬基酚聚氧乙烯醚(NP-10)合成新工艺流程 教育部科技进步二等奖
个人的奖项有:1995年 光华科技基金奖三等奖; 1997年 "大连市优秀专家"称号; 在读硕士、博士人数:硕士生5名,博士生5名;已毕业硕士博士人数:硕士生24名,博士生9名。
本人带领的研究组是“精细化工国家重点实验室”的组成之一,是一个老中青结合、以中青年学术骨干为主的、学术思想活跃的研究集体,而且是一个有广泛国际合作传统的研究集体,先后与德国日本开展多项合作研究和联合培养博士生。2001年与德国Wuppertal大学O.Stelzer教授共同承担德国DFG基金项目,2002年将派送博士生去MPI fuer Kohlenforsdhung与H.Boennemann教授联合培养。共招收博士生14名、硕士生29名,目前有五名博士生和五名硕士生在读。
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金子林
,-0001,():
-1年11月30日
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金子林, Yanhua Wang, Jingyang Jiang, Qiang Miao, Xiaowei Wu, Zilin Jin*
Catalysis Today 74(2002)85-90,-0001,():
-1年11月30日
Nonionic tensioactive water-soluble phosphines that act as ligands for rhodium-catalyzed hydroformylation of higher olefins under aqueous-organic biphasic conditions are described with emphasis on the recycling efficiency of homogeneous catalyst. Phosphines discussed are P-[p-C6H4(OCH2CH2)nOH]3 (1a: N=3n=18, 1b: N=3n=25) and Ph2P-[p-C6H4(OCH2CH2)nOH] (2a: N=n=16, 2b: N=n=25) (PEO-TPPs). The rhodium catalyst combined with these ligands gave an average turnover frequency (TOF) of 182h-1 for 1-hexene. More importantly, recovery and reuse of catalyst is possible because of the inverse temperature-dependent water solubility of the phosphines.
Nonionic phosphine, Homogeneous catalyst, Environmentally benign catalysis, Separation, Hydroformylation
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【期刊论文】Thermoregulated liquid/liquid biphasic catalysis and its application
金子林, Yanhua Wang, Jingyang Jiang, and Zilin Jin*
Catalysis Surveys from Asia, Vol. 8, No.2, June 2004,-0001,():
-1年11月30日
A brief overview of our recent research results of thermoregulated liquid/liquid biphasic catalysis is presented. Emphasis is given to the general principles of thermoregulated phase-transfer catalysis (TRPTC) and thermoregulated phase-separable catalysis (TPSC). In addition, the applications of TRPTC and TPSC in biphasic catalysis are also discussed. The introduction of TRPTC to biphasic system is free from the shortcomings of classical aqueous/organic two-phase catalysis, in which the application scope is restrained by the water solubility of the substrate. Meanwhile, TPSC provides a very simple and reliable way to deal with the separation of catalyst in homogeneous catalysis. The common advantages of TRPTC and TPSC are characterized by homogeneous catalysis coupled with convenient biphasic separation.
thermoregulated ligands, thermoregulated phase-transfer catalysis, thermoregulated phase-separable catalysis, hydroformylation, hydrogenation.,
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金子林, Chun Liu, Jingyang Jiang, Yanhua Wang, Fang Cheng, Zilin Jin*
Journal of Molecular Catalysis A: Chemical 198(2003)23-27,-0001,():
-1年11月30日
A novel water soluble phosphine, N,N-dipolyoxyethylene-substituted-2-(diphenylphosphino)phenylamine (PEO-DPPPA), was synthesized by a two-step ethoxylation of 2-(diphenylphosphino)phenylamine (2-Ph2P-C6H4NH2, DPPPA). In the first step, DPPPA was ethoxylated without catalyst to give an intermediate with an average polyethylene glycol (PEG) chain length (L=m+n) of 3. Thereafter, this intermediate was further ethoxylated by using KOH as a catalyst to obtain the products with needed values of L. The solubility of the products in water increases with increasing of L. When L is more than 35, the products are water-soluble and possess the property of inverse temperature-dependent solubility in water (cloud point, Cp) as nonionic surfactants. The PEO-DPPPA/Rh complex catalyst formed in situ by RhCl3·3H2O and PEO-DPPPA (L=45) has been applied to the aqueous-organic biphasic hydroformylation of 1-decene. The conversion of olefin and the yield of aldehyde are 99.5 and 99.0%, respectively, under the conditions of 120℃, 5.0MPa (CO/H2=1), P/Rh=4 (molar ratio), 1-decene/Rh=1000 (molar ratio) and 5 h. Recycling test shows that both the conversion of olefin and the yield of aldehyde are still higher than 94.0% even after the catalyst has been recycled 20 times. The high reactivity of PEO-DPPPA/Rh complex can be attributed to a process termed thermoregulated phase transfer catalysis.
Thermoregulated phase transfer catalysis, Hydroformylation, Thermoregulated phosphine, High olefins
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金子林, Yanhua Wang, Jingyang Jiang, Rong Zhang, Xiaohang Liu, Zilin Jin*
Journal of Molecular Catalysis A: Chemical 157(2000)111-115,-0001,():
-1年11月30日
Application of the concept of critical solution temperature (CST) of nonionic tensioactive phosphine ligand P[p-C6H4O (CH2CH2)O)nH)3 (PETPP) in the hydroformylation of higher olefins in organic monophase system is presented for the first time. The PETPPrRh complex catalyst is insoluble in organic solvent at room temperature T<CST., on heating to the temperature T>CST, the catalyst would be soluble in organic solvent. Thus, the catalytic reaction would have taken place homogeneously at the reaction temperature (T>CST). When the reaction is completed, on cooling to the room temperature (T<CST), the catalyst would precipitate out from the organic solvent, and could be easily separated from the product and recycled efficiently. Hydroformylation of higher olefins catalyzed by PETPP/Rh complex in organic monophase system is investigated. Under the conditions of T=130℃, P=4.0MPa, the conversion of 1-dodecene and yield of the aldehyde are 95.8% and 93.7%, respectively.
Critical solution temperature, Nonionic tensioactive phosphine ligand, Organic monophase system, Higher olefins, Rhodium, Hydroformylation
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金子林, Jingyang Jiang, Yanhua Wang, Chun Liu, Qimin Xiao, Zilin Jin*
Journal of Molecular Catalysis A: Chemical 171(2001)85-89,-0001,():
-1年11月30日
A novel water soluble phosphine, N,N-dipolyoxyethylene-substituted-4-(diphenylphosphino) benzenesulfonamide (PEODPPSA), is synthesized by ethoxylation of 4-(diphenylphosphino) benzenesulfonamide Ph2P-C6H4SO2NH2 (DPPSA) obtained from palladium-catalyzed P-C coupling reaction between 4-I-C6H4SO2NH2 and Ph2PH. The PEO-DPPSA possesses the same property of inverse temperature-dependent solubility in water (cloud point, Cp) as nonionic surfactants. Investigation on the behavior of RhCl3
Nonionic water-soluble phosphine, Thermoregulated phase transfer catalysis, Hydroformylation, 1-Decene, Cloud point
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金子林, Jinayang Jiang, Yanhua Wang, Chun Liu, Fushe Han, Zilin Jin*
Journal of Molecular Catalysis A: Chemical 147(1999)131-136,-0001,():
-1年11月30日
A series of nonionic surface-active phosphine ligands with the general formula, [RO(CH2CH2O)-n]-m PPh3-m(m=1,2), (AEOPP).has been synthesized. Cloud points of the phosphine ligands are measured and effects of changing hydrophilic and lipophilic groups on the cloud point of the phosphine ligand are examined. Experiment shows that AEOPP has distinct cloud point when n is greater than 7, R group larger than butyl and EO/Cj ratio greater than 0.5 (where EO=n
Nonionic surface-active phosphine, Cloud point, Thermoregulated phase transfer ligands, Hydroformylation, Higher olefins
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金子林, Yanhua Wang, Jingyang Jiang, Xiaowei Wu, Fang Cheng, and Zilin Jin*
Catalysis Letters Vol. 79, Nos.1-4, April 2002,-0001,():
-1年11月30日
Based on the critical solution temperature of nonionic tensioactive phosphine ligand, a novel process termed as tfiermoregulated phase-separable catalysis has been applied for the first time in the hydroformylation of cyclohexene. The catalyst is formed in situ from P[p-C6H4O(CH2CH2O)n]3 (PETPP) and RfiCl3·3H2O. Under the conditions of T=130℃, P=5.0Mpa, the conversion of cyclohexene and yield of aldehyde are 98.4%. The catalyst was reused four times and no loss in activity has been observed.
nonionic phosphine, critical solution temperature, hydroformylation, thermoregulated phase-separable catalyst, rhoditm.,
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金子林, Xiaolai Zheng, Jingyang Jiang, Xiaozhong Liu, Zilin Jin*
Catalysis Today 44(1998)175-182,-0001,():
-1年11月30日
A series of poly (ethylene oxide)-substituted triphenylphosphines, Ph3-mP[C6H4-p-(OCH2CH2)nOH]m (PEO-TPPs; 1a m-1, 1b m-2, 1c m-3; N=m×n-8-25), have been prepared by the ethoxylation of mono-, di-, and tri-p-hydroxytriphenylphosphines. PEO-TPPs demonstrate an inverse temperature-dependent solubility in water, and possess distinct cloud points range from 26℃ to 90℃. Based on the clouding property of PEO-TPPs, a new line of aqueous/organic two-phase catalysis termed the thermoregulated phase-transfer catalysis (TRPTC) has been described. That is, the catalyst transfers into the organic phase to catalyze a reaction at a higher temperature, and returns to the aqueous phase to be separated from the products at a lower temperature. Application of this novel strategy to the rhodium-catalyzed two-phase hydroformylation of higher olefins gave desirable results with an average turnover frequency of 180h-1 for 1-dodecene. The TRPTC is suitable for carrying out a reaction with extremely water-immiscible substrate in the aqueous/organic two-phase system. Thus, the application scope of the classical two-phase catalysis has been widened.
Water-soluble ligand, Two-phase catalysis, Thermoregulated phase-transfer catalysis, Poly(, ethylene oxide), -substituted triphenylphosphine, Hydroformylation, Higher olefin
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金子林, Ruifang Chen, Xiaozhong Liu, Zilin Jin*
Journal of Organometallic Chemistry 571(1998)201-204,-0001,():
-1年11月30日
A novel nonionic water-soluble octylpolyglycol-phenylene-phosphite (OPGPP) was synthesized and the two-phase hydroformylation of styrene catalyzed by an OPGPP: Rh catalyst was investigated fully. The catalyst displayed excellent catalytic activity; high styrene conversion and high aldehyde yield (99.6 and 99.3%, respectively) were obtained at 80℃ and 5.0MPa, and the molar ratio of branched:normal aldehyde was 4.8. The experimental results revealed that there was a 'thermoregulated phase-transfer catalysis (TRPTC)' process present in the reactions.
Water-soluble phosphine, Two-phase hydroformylation, Styrene, TRPTC
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