有机稀土金属催化剂的制备及应用研究
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摘要
采用氧化镧、氧化钕、氧化钇与浓盐酸反应制成其相应的氯化物,分别与皂化过的新癸酸和异辛酸反应制备出6种有机稀土金属羧酸盐,并分别用于催化ε-己内酯开环聚合,聚合物利用GPC与1H NMR表征,实验结果表明:新癸酸镧、新癸酸钕、异辛酸镧、异辛酸钕均有一定的催化效应,能够制备满足各种应用的低分子量PCL低聚物.
This research used lanthanum oxide,neodymium oxide and yttrium oxide to react with strong hydrochloric acid and produce the corresponding chloride,and after saponification reacted respectively with neo-decanoic acid and 2-Ethylhexanoic acid to prepare six kinds of organic rare earth metal carboxylates. They were respectively used in catalytic epsilon-caprolactone ring-opening polymerization,and polymers using GPC and ~1H NMR characterization. The results show that the new decanoic acid lanthanum,new decanoic acid neodymium,lanthanum and neodymium iso-octanate all have certain catalytic effect,and can satisfy the preparation of low-molecular-weight PCLS oligomers.
This research used lanthanum oxide,neodymium oxide and yttrium oxide to react with strong hydrochloric acid and produce the corresponding chloride,and after saponification reacted respectively with neo-decanoic acid and 2-Ethylhexanoic acid to prepare six kinds of organic rare earth metal carboxylates. They were respectively used in catalytic epsilon-caprolactone ring-opening polymerization,and polymers using GPC and ~1H NMR characterization. The results show that the new decanoic acid lanthanum,new decanoic acid neodymium,lanthanum and neodymium iso-octanate all have certain catalytic effect,and can satisfy the preparation of low-molecular-weight PCLS oligomers.
引文
[1]董海峰,吴启勋.镧系元素物理化学性质的定量构效关系研究[J].青海师范大学学报(自科版),2006(2):80-83.
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[5]郁楠,侯召民,席振峰.阳离子型稀土金属有机化合物[J].化学进展,2008,20(10):1515-1523.
[6] KAMINSKY W. Metalorganic Catalysts for Synthesis and Polymerization:Recent Results by Ziegler-Natta and Metallocene Investigations[M]. Polymer Science,1999.
[7]刘瑞婷.稀土有机化合物的新反应研究[D].上海:复旦大学,2006.
[8]罗成文,王正平,郑成.稀土有机配合物的研究与应用[J].广州化工,2010,38(3):26-29.
[9] ATHANASION K A,AGRAWAL C M,BARBER F A,et al. Orthopaedic applications for PLA-PGA biodegradable polymers.[J]. Arthroscopy the Journal of Arthroscopic&Related Surgery,1998,14(7):726-737.
[10] KRICHELDORF H R. Syntheses and application of polylactides[J]. Chemosphere,2001,43(1):49-54.
[11]邓冰锋,黄从树,叶章基,等.己内酯的开环聚合与应用研究[J].材料开发与应用,2012(6):72-77.
[12]胡芸,谢凯,陈一民,等.ε-己内酯聚合反应的研究[J].高分子材料科学与工程,2002,18(6):48-50.
[13]解德良,杨昌正.羟基酸引发ε-己内酯开环聚合的研究[J].高分子学报,2000,1(5):532-537.
[14] SCHINDLER A,HIBIONADA Y M,PITT C G. Aliphatic polyesters. III. Molecular weight and molecular weight distribution in alcohol‐initiated polymerizations ofε-caprolactone[J]. Journal of Polymer Science Polymer Chemistry Edition,1982,20(20):319-326.
[15] KRICHELDORF H R,BERL M,SCHARNAGL N. Poly(lactones). 9. Polymerization mechanism of metal alkoxide initiated polymerizations of lactide and various lactones[J]. Macromolecules,1988,21(2):286-293.
[16] KRICHELDORF H R,STRICKER A,LANGANKE D. Polylactones,50. The reactivity of cyclic and noncyclic dibutyltin bisalkoxides as initiators in the polymerization of lactones[J]. Macromolecular Chemistry&Physics,2001,202(12):2525-2534.
[17]陈剑华.一种环保新癸酸钕的制备方法:CN105348073A[P]. 2016-02-24.
[2]吴启勋.镧系元素的失屏参数及应用[J].化学通报,1984(3):24-26.
[3] ZHANG L F,Yu C P,SHEN Z Q. Characteristics linetics and mechanism of caprolactone polymerization by lanthanide tris(2,6-dimethylphenolate)s[J]. Polymer Bulletin,2003,51:47-53.
[4] YU C P,ZHANG L F,SHEN Z Q. Ring-opening polymerization of 2,2-dimethyltrimethylene carbonate using rare earth tris(4-tertbutylphenolate)s as a singel component initiator[J]. Journal of Molecular Catalysis A:Chemical,2004,212(1-2):365-369.
[5]郁楠,侯召民,席振峰.阳离子型稀土金属有机化合物[J].化学进展,2008,20(10):1515-1523.
[6] KAMINSKY W. Metalorganic Catalysts for Synthesis and Polymerization:Recent Results by Ziegler-Natta and Metallocene Investigations[M]. Polymer Science,1999.
[7]刘瑞婷.稀土有机化合物的新反应研究[D].上海:复旦大学,2006.
[8]罗成文,王正平,郑成.稀土有机配合物的研究与应用[J].广州化工,2010,38(3):26-29.
[9] ATHANASION K A,AGRAWAL C M,BARBER F A,et al. Orthopaedic applications for PLA-PGA biodegradable polymers.[J]. Arthroscopy the Journal of Arthroscopic&Related Surgery,1998,14(7):726-737.
[10] KRICHELDORF H R. Syntheses and application of polylactides[J]. Chemosphere,2001,43(1):49-54.
[11]邓冰锋,黄从树,叶章基,等.己内酯的开环聚合与应用研究[J].材料开发与应用,2012(6):72-77.
[12]胡芸,谢凯,陈一民,等.ε-己内酯聚合反应的研究[J].高分子材料科学与工程,2002,18(6):48-50.
[13]解德良,杨昌正.羟基酸引发ε-己内酯开环聚合的研究[J].高分子学报,2000,1(5):532-537.
[14] SCHINDLER A,HIBIONADA Y M,PITT C G. Aliphatic polyesters. III. Molecular weight and molecular weight distribution in alcohol‐initiated polymerizations ofε-caprolactone[J]. Journal of Polymer Science Polymer Chemistry Edition,1982,20(20):319-326.
[15] KRICHELDORF H R,BERL M,SCHARNAGL N. Poly(lactones). 9. Polymerization mechanism of metal alkoxide initiated polymerizations of lactide and various lactones[J]. Macromolecules,1988,21(2):286-293.
[16] KRICHELDORF H R,STRICKER A,LANGANKE D. Polylactones,50. The reactivity of cyclic and noncyclic dibutyltin bisalkoxides as initiators in the polymerization of lactones[J]. Macromolecular Chemistry&Physics,2001,202(12):2525-2534.
[17]陈剑华.一种环保新癸酸钕的制备方法:CN105348073A[P]. 2016-02-24.