Ph_3P催化丙炔酰胺的加成聚合及其聚合物结构表征
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摘要
本论文研究的主要内容是Ph_3P催化丙炔酰胺的加成聚合,包括聚合过程研究、聚合产物的结构表征、性能测试及聚合机理的初步探讨。
以红外、~1H-NMR、~(13)C-NMR以及时间飞行质谱(MALDI-TOF)等测试方法对聚合物进行表征。结果表明丙炔酰胺在Ph_3P亲核试剂催化下发生碳碳叁键与氨基的加成聚合反应,从而得到超支化聚丙炔酰胺。研究了聚合反应条件(如溶剂、温度和单体与Ph_3P摩尔比等)对聚合的影响。得到的聚合物的分子量在600-900范围内(聚合度为9-13);极性增大、温度升高,聚合物产率降低;催化剂与单体摩尔比增加,产率增大。
对聚丙炔酰胺进行了初步性能测试,该聚合物具有荧光特性。
通过聚合过程分析以及产物表征可以得到,Ph_3P进攻炔键使酰胺氮原子上氢发生质子转移(包括分子间或分子内)。整个过程为亲核加成-质子转移-逐步聚合过程。
The addition polymerization of propiolamide catalyzed by Ph_3P was discussed, including the process of polymerization, the structures and properties of the polypropiolamide and the mechanism of the polymerization.
The results of FT-IR,~1H-NMR ~(13)C-NMR and MS showed: the reaction of alkynoates and amides in propiolamide in the presence of Ph_3P proceeds and the hyperbranched polypropiolamide is obtained finally. Different reaction conditions such as monomer concentrations, temperatures and solvents were also discussed. The molecular weight of the polypropiolamide was 600-900(the degree of the polymerization was 9-13). The yield of polymer decreased with the temperature's rising, the molar rate's increasing of Ph_3P and monomer and the polarity's heightening of solvents.
What's more, our primary test showed that the hyperbranched polymer prepared is blessed with fluorescent properties.
The analysis of the process of the polymerization and the primary characteristic of the polymer indicated that intermolecular and intramolecular proton transfer of the hydrogen on the amido group happened when Ph_3P attacked alkynoates. The whole process of the polymerization included nucleophilic addition, proton transfer and step reaction polymerization.
以红外、~1H-NMR、~(13)C-NMR以及时间飞行质谱(MALDI-TOF)等测试方法对聚合物进行表征。结果表明丙炔酰胺在Ph_3P亲核试剂催化下发生碳碳叁键与氨基的加成聚合反应,从而得到超支化聚丙炔酰胺。研究了聚合反应条件(如溶剂、温度和单体与Ph_3P摩尔比等)对聚合的影响。得到的聚合物的分子量在600-900范围内(聚合度为9-13);极性增大、温度升高,聚合物产率降低;催化剂与单体摩尔比增加,产率增大。
对聚丙炔酰胺进行了初步性能测试,该聚合物具有荧光特性。
通过聚合过程分析以及产物表征可以得到,Ph_3P进攻炔键使酰胺氮原子上氢发生质子转移(包括分子间或分子内)。整个过程为亲核加成-质子转移-逐步聚合过程。
The addition polymerization of propiolamide catalyzed by Ph_3P was discussed, including the process of polymerization, the structures and properties of the polypropiolamide and the mechanism of the polymerization.
The results of FT-IR,~1H-NMR ~(13)C-NMR and MS showed: the reaction of alkynoates and amides in propiolamide in the presence of Ph_3P proceeds and the hyperbranched polypropiolamide is obtained finally. Different reaction conditions such as monomer concentrations, temperatures and solvents were also discussed. The molecular weight of the polypropiolamide was 600-900(the degree of the polymerization was 9-13). The yield of polymer decreased with the temperature's rising, the molar rate's increasing of Ph_3P and monomer and the polarity's heightening of solvents.
What's more, our primary test showed that the hyperbranched polymer prepared is blessed with fluorescent properties.
The analysis of the process of the polymerization and the primary characteristic of the polymer indicated that intermolecular and intramolecular proton transfer of the hydrogen on the amido group happened when Ph_3P attacked alkynoates. The whole process of the polymerization included nucleophilic addition, proton transfer and step reaction polymerization.
引文
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[2]唐黎明.新型功能性超支化聚酯的合成及表征[J].高等学校化学学报,2001,22(6):1073-1075.
Flory.Molecular size distribution in three-dimensional Polymers Ⅵ.Branched Polymer Containing A-R-Bf-1-type Unit s[J].J Am Chem Soc,1952,74(11):2718-2723.
[3]王学川,强涛涛,任龙芳.超支化聚合物的研究进展及其在皮革工业中的应用前景[J].中国皮革,2005,34(9):14-19.
[4]陈梦茹,金养智.超支化聚合物[J].热固性树脂,2003,18(1):24-27.
[5]Kim Y H.J.Lyot ropic liquid crystalline hyper-branched aromatic polyamides[J].Am Chem.Soc.,1992,114(12):4947-4948.
[6]Ishida Y,Sun ACF,Jikei M,Kakimoto M.Synthesis of Hyper-branched Aromatic Polyamide Starting from Dendrons as ABx Monomers:Effect of Monomer Multiplicity on the Degreed of Branching[J].Macromolecules,2000,33(8):2832-2832.
[7]Gang Yang,Mit sutoshi,and Masa-aki Kakimoto.Synthesis and Properties of Hyperbranched Aromatic Polyamide[J].Macromolecules,1999,32(7):2215-2220.
[8]V R Reichert,L J Mathias.Tetrahedrally-Oriented Four-Armed Star and Branched Aramids[J].Macromolecules,1994,27(24):7024-7029.
[9]于世钧,赵洪霞,李锐生.新型超支化聚芳酰胺的合成及表征[J].化学通报,2003,(12):843-849.
[10]M J ikei,S H Chon,M Kakimoto.Synthesis of Hyper-branched Aromatic Polyamide f rom AromaticDiamines and Trimesic Acid[J].Macromolecules,1999,32(6):2061-2064.
[11]Ryoji Nomura;Yasunori Fukushima;Hideo Nakako;and Toshio Masuda.Conformational Study of Helicai Poly-(propiolic esters) in Solution[J].J.Am.Chem.Soc.2000,122(37),8830-8836.
[12]Irfan Saeed;Masashi Shiotsuki;and Toshio Masuda.Remarkable Cocatalytic Effect of Alkalic Metal Amides and Alkoxides in the Rhdium-Catalyzed Polymerization of Phenylacetylene[J].Macromolecules 2006,39(16),5347-5351.
[13]赵进,程金生,黄祖良.钯催化下丙炔酸乙酯的区域选择性环三聚芳构化反应研究[J].湘潭大学自然科学学报.2007,29(3):88-92.
[14]Maitlis P M.Convenient palladium—catalyzed cyclotfimerization of alkynes[J].Acc Chem Res,1976,9(3):93.
[15]Kelley E A,Maiflis P M.rift-and tetra-nuclear homo-or hetero-metallic palladium(11)and platinum(11)complexeswith double ha1.ide bridges:molecular structure of[NBu_4]_2[(C_6)_2Pt(-el)_2Pt(-Cl)_2Pt(C_6F_5)_2][J].J Chem Soc,Dalton Trans,1979,22(I):167-168.
[16]Stone F G,West R.1ntramolecular palladium—catalyzed aryl amination and aryl amidation[J].Adv Organamet Chem,1975,13(4):363-364.
[17]Pena D,POTez,Guitl No.n E.Palladium—catalyzed tr/merization of strained cycloalkynes:synthesis of decacyclene[J].Org Lett,1999,1(10):1555-1556.
[18]Yamamota Y,Nagata A,hoh K.Highly trons-selective intramolecularpinacol coupling of dials catalyzed by bulky Cp_2TiPh[J].Tetrahedron.1999,40(5):5035-5036.
[19]施志坚,聂玲清,曹卫国.DBU及DBN与丙炔酸甲酯的迈克尔型加成及其产物的核磁共振谱学研究[J].分析科学学报,2004,20(6):586-588.
[20]倪志刚.强有机碱试制剂DBU和DBN在有机合成中的应用[J].中国医学工业杂志,1991.22(4):180-186
[21]Michel Perbost,Marc Lucas,Claude Chavis,Jean—Louis Imbach.Unusual reaction of 1,8-diazabicyelo-[5.4.0]undec-7-ene with diethyl maleate[Jl.J.Heterocyclic.Chem.,1993,30:627-629
[22]聂玲清,施志坚.DBU与全氟炔酸酯de迈克尔型加成及其产物的NMR谱学研究[J]波谱学杂志,2002,19(4):377-384
[23]丁维钰,曹卫国,徐振蒙.膦、胂叶立德的化学与应用(ⅪⅤ)[J].高等学校化学学报,1990,11(11):1212-1217.
[24](a) Kuroda,H.;Tomita,I.;Endo,T.A Novel Polyaddition of Diols with Bifunctional Acetylenes Having Electron-Withdrawing Groups[J].Macromolecules 1995,28(2),433-434;
(b) Kuroda,H.Tomita,I.;Endo,T.A Novel Polyaddition of Diols with Bifunctional Acetylenes Having Electron-Withdrawing Crroups[J].Macromolecules 1995,28(18),6020-6021.
[25]Aoki,K.;Kakudate,Y.;Yoshida,M.;Usuba,S.:Fujiwara,S.Solid-state polymerization of acetylene under pressure[J].Synthetic Metals.1989,28(3),D91-D98.
[26]James C.Byrd,Michelle A.Hartman,Jodi L.Kreiling,Richard G.MacDonald.High-affinity ligand binding by wild-type/mutant heteromeric complexes of the mannose 6-phosphate/insulin-like growth factor Ⅱ receptor[J].FEBS Journal.2009,276(7):1915-1929.
[27]Carlini,C.;Chien,J.C.W.Semiconducting poly-(monocyanoacetylenes)[J].J.Polym.Sci.,Polym.Chem.Ed.1984,22(11),2749-2766.
[28]C.Carlini,L.Flamigni,F.Barigelletti,P.Bortolus.Photophysical study on a new class of benzophenone containing photoinitiators of polymerization:Properties of poly(4-acryloxybenzophenone) and a model compound.European Polymer Journal.1984,20(2) 171-175.
[29]Francesco Cognetti,Paula Pinnaro,Paolo Carlini,Ettore M.Conti,Massimo Cortese,Camillo F.Pollera.Randomized open cross-over trial between Metoclopramide(MCP) and dexamethazone(DXM) for the prevention of cisplatin-induced nausea and vomiting.European Journal of Cancer and Clinical Oncology.1984,20(2):183-187.
[30]Deits,W.;Cukor,P.;Rubner,M.;Jopson,H.Analogs ofpolyacetylene.Preparation and properties[J].Ind.Eng.Chem.Prod.Res.Dev.1981,20(4),696-704.
[31]Armand F.Miranda,Salvatore DiMauro,Saburo Sakoda,Eric A.Schon,Serenella Servidei,Sara Shanske,Massimo Zeviani,John M.Opitz,James F.Reynolds.Metabolic myopathies.American Journal of Medical Genetics.1986,25(4):635-651.
[32]H.Fukuda,S.Brailowsky,C.Menini,C.Silva-Barrat,D.Riche,R.Naquet.Anticonvulsant effect of intracortical,chronic infusion of GABA in kindled rats:Focal seizures upon withdrawal.Experimental Neurology.1987,98(1):120-129.
[33]Fukuda,S.;Takahashi,A.;Tsukamoto,J.Structure of HNO_3-intercalated graphite fiber prepared from cyanoacetylene[J].Synth.Met.1988,23(1-4),475-480.
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