胡爱国教授研究组

 

20165月,在为《高分子学报》期刊撰写专论时萌生了总结现有高分子合成方法的念头,希望为新进入这个领域的学生提供一些参考。高分子化学的进展可谓是日新月异,有些聚合反应方法在相当长的时间里是被归属于逐步聚合反应的,但近年来却有人通过机理转变等方法将其转为链式聚合反应(如Kumada缩合聚合反应);有些聚合反应堪要被高分子科学主流抛弃,但还有人顽强坚守住这块阵地,拓展出了新的发展空间(如Bergman环化聚合反应);而一些经典的有机合成反应也于近年华丽转身为高分子合成反应(如Click反应)。有鉴于此,对聚合反应的综合和细分是一件非常困难的事。

 

以下这个表可看作是这种尝试的1.0版本(也许早有人做过类似的事,但重要的事情多说几遍也无妨)。可以肯定的一点是,它至少涵盖了目前高分子合成方法学七成以上的内容。所列参考文献只说明该文献里涉及到了这种聚合反应,不代表该文献在该领域的权威性。如果对这种聚合反应方法感兴趣,可籍此文献通过引用网络的方式找到最合适的文献。

 

如果您发现下表中分类有缺失、含混、错误等情况,请联系我,非常感谢!我将及时予以订正。

 

反应大类

反应小类

聚合反应细分

代表单体

文献

链式聚合反应

自由基聚合反应

传统自由基聚合反应

苯乙烯,MMAEAEPA,丙烯腈等

1-6

ATRP

苯乙烯,丙烯腈,丙烯酸酯,丙烯酰胺等

7-9

RAFT

苯乙烯,丙烯酸酯,丁二烯,丙烯腈等

10-13

NMRP

苯乙烯,丙烯酸酯

14-16

阴离子聚合反应

 

苯乙烯,异戊二烯

17-19

配位聚合反应

 

乙烯,丙烯,多取代烯烃

20-25

 

α-烯烃

25-27

 

二烯

28-30

 

炔烃

31-34

 

异腈

35-37

 

噻吩

38-40

阳离子聚合反应

 

苯乙烯,异丁烯

41-44

 

苯甲醛,丁酮

45-48

开环聚合反应

开环复分解聚合反应

降冰片烯,二环庚二烯,环戊烯,二环戊二烯,环辛烯

49-52

环酯开环聚合反应

己内酯,丙交酯,丁内酯,环碳酸酯,环磷酸酯

53-55

环醚开环聚合反应

环氧乙烷,环氧丙烷,四氢呋喃

56,57

环胺开环聚合反应

氮丙啶,氮杂环丁烷

58,59

环酰胺开环聚合反应

己内酰胺,β-内酰胺,β-内酰胺糖

60-62

环内酸酐开环聚合反应

NCAN-取代NCA

63-65

环缩醛开环聚合反应

三聚甲醛,二氧戊环

66,67

环硫化物开环聚合反应

环硫乙烷,环硫丙烷,硫化异丁烯,多环烯丙基硫化物

68-70

硅杂环开环聚合

环二甲基硅烷

71,72

逐步聚合反应

缩合聚合反应(有小分子副产物生成)

氧化聚合反应

苯并噻吩,乙烯二氧噻吩,3-己基噻吩,咔唑

73-76

直接芳香化聚合反应

辛氧基噻吩,二辛基-二溴代芴3-己基噻吩,联噻吩;多卤代芳烃

77,78

Suzuki 反应

四溴芘,四溴苯基苯,均三溴苯;联苯二硼酸,二硼酸酯,二硼酸

79-81

Kumada反应

芳基卤,芳基格氏试剂。注:部分属于链式聚合

82-84

Sonogashira 反应

三乙炔基苯,对二溴苯

85-88

Heck反应

烯烃,芳基卤

89-91

Stille反应

芳基三丁基锡,芳基卤

92

Negishi反应

芳基锌试剂,芳基卤

93

Yamamoto 反应

多卤代芳烃

94-96

Ullman反应

多卤代芳烃

97-99

Schiff 碱反应

对苯二胺,均苯三羧酸

100-102

尼龙66及类似物的合成

己二胺,己二酸

103-105

聚酰亚胺-缩聚反应

均苯四甲酸酐+对苯二胺

106-108

PET合成-缩聚反应

对苯二甲酸+乙二醇

109-111

芳族取代反应

双酚A的钠盐+44‘-二氯代二苯基砜

112,113

氧化偶合反应

氧气+26-二甲基苯酚

114-116

MCP (Ugi, Passerini, Biginelli, Kabachnik-Fields反应)

异氰++羧酸

117-120

FriedelCrafts反应

芳烃,二甲氧基甲烷

121-123

偶联聚合反应(无小分子副产物生成)

Bergman环化反应

烯二炔

124-126

环三聚反应

炔烃,腈

127-129

聚氨酯、聚脲的合成

二异氰酸酯,多元醇,多元胺

130-132

聚噻嗪的合成

异腈,二烷基丁炔二酸酯 ,硫脲嘧啶

133-135

二氧化碳参与聚合反应

二氧化碳,环氧,氮丙啶

136-140

环氧树脂的固化

酸酐、环氧氯丙烷;环氧氯丙烷、双酚A

141-143

Click聚合反应

多叠氮,多炔烃

144,145

Diels-Alder反应

炔烃,环戊二烯酮

146-148

 

参考文献:

         (1)    Dossi, M.; Storti, G.; Moscatelli, D. "Relevance of backbiting and beta-scission reactions in the free radical polymerization of Acrylonitrile". Macromolecular Symposia 2010, 289, 119.

         (2)    Furuncuoğlu, T.; Uğur, İ.; Değirmenci, İ.; Aviyente, V. "Role of Chain Transfer Agents in Free Radical Polymerization Kinetics". Macromolecules 2010, 43, 1823.

         (3)    Greesh, N.; Hartmann, P. C.; Sanderson, R. D. "Preparation of Polystyrene/Clay Nanocomposites by Free-Radical Polymerization in Dispersion". Macromolecular Materials and Engineering 2009, 294, 787.

         (4)    Yilmaz, G.; Aydogan, B.; Temel, G.; Arsu, N.; Moszner, N.; Yagci, Y. "Thioxanthone−Fluorenes as Visible Light Photoinitiators for Free Radical Polymerization". Macromolecules 2010, 43, 4520.

         (5)    Zetterlund, P. B.; Thickett, S. C.; Perrier, S.; Bourgeat-Lami, E.; Lansalot, M. "Controlled/Living Radical Polymerization in Dispersed Systems: An Update". Chemical Reviews 2015, 115, 9745.

         (6)    Zhang, G.; Song, I. Y.; Ahn, K. H.; Park, T.; Choi, W. "Free Radical Polymerization Initiated and Controlled by Visible Light Photocatalysis at Ambient Temperature". Macromolecules 2011, 44, 7594.

         (7)    Matyjaszewski, K. "Atom Transfer Radical Polymerization (ATRP): Current Status and Future Perspectives". Macromolecules 2012, 45, 4015.

         (8)    Vieira, R. P.; Ossig, A.; Perez, J. M.; Grassi, V. G.; Petzhold, C. L.; Peres, A. C.; Costa, J. M.; Lona, L. M. F. "Styrene ATRP using the new initiator 2,2,2-tribromoethanol: Experimental and simulation approach". Polymer Engineering & Science 2015, 55, 2270.

         (9)    Zhang, L.; Miao, J.; Cheng, Z.; Zhu, X. "Iron-Mediated ICAR ATRP of Styrene and Methyl Methacrylate in the Absence of Thermal Radical Initiator". Macromolecular Rapid Communications 2010, 31, 275.

         (10)  Gonçalves, M. A. D.; Pinto, V. D.; Dias, R. C. S.; Hernándes-Ortiz, J. C.; Costa, M. R. P. F. N. "Dynamics of Network Formation in Aqueous Suspension RAFT Styrene/Divinylbenzene Copolymerization". Macromolecular Symposia 2013, 333, 273.

         (11)  Hlalele, L.; D’hooge, D. R.; Dürr, C. J.; Kaiser, A.; Brandau, S.; Barner-Kowollik, C. "RAFT-Mediated ab Initio Emulsion Copolymerization of 1,3-Butadiene with Acrylonitrile". Macromolecules 2014, 47, 2820.

         (12)  Rieger, J.; Zhang, W.; Stoffelbach, F.; Charleux, B. "Surfactant-Free RAFT Emulsion Polymerization Using Poly(N,N-dimethylacrylamide) Trithiocarbonate Macromolecular Chain Transfer Agents". Macromolecules 2010, 43, 6302.

         (13)  Zhang, X.; Boisson, F.; Colombani, O.; Chassenieux, C.; Charleux, B. "Synthesis of Amphiphilic Poly(acrylic acid)-b-poly(n-butyl acrylate-co-acrylic acid) Block Copolymers with Various Microstructures via RAFT Polymerization in Water/Ethanol Heterogeneous Media". Macromolecules 2014, 47, 51.

         (14)  Kaim, A.; Pietrasik, K.; Stokłosa, T. "N,N-Diaminoethane linked bis-TEMPO-mediated free radical polymerization of styrene". European Polymer Journal 2010, 46, 519.

         (15)  Lang, A. S.; Neubig, A.; Sommer, M.; Thelakkat, M. "NMRP versus “Click” Chemistry for the Synthesis of Semiconductor Polymers Carrying Pendant Perylene Bisimides". Macromolecules 2010, 43, 7001.

         (16)  Messerschmidt, M.; Millaruelo, M.; Komber, H.; Häussler, L.; Voit, B.; Krause, T.; Yin, M.; Habicher, W. D. "Synthesis of Partially Protected Block Copolymers Based on 4-Hydroxystyrene Using NMRP and a Sequence of Polymer Analogous Reactions". Macromolecules 2008, 41, 2821.

         (17)  Carlotti, S.; Desbois, P.; Warzelhan, V.; Deffieux, A. "Retarded anionic polymerization (RAP) of styrene and dienes". Polymer 2009, 50, 3057.

         (18)  Nakahara, A.; Satoh, K.; Saito, H.; Kamigaito, M. "Intramolecular friedel-crafts cyclization and subsequent hydrogenation of styrene-isoprene random copolymers prepared by anionic polymerization for thermally-resistant and optical applications". Journal of Polymer Science Part A: Polymer Chemistry 2012, 50, 1298.

         (19)  Vijayaraghavan, R.; Pringle, J. M.; MacFarlane, D. R. "Anionic polymerization of styrene in ionic liquids". European Polymer Journal 2008, 44, 1758.

         (20)  Delferro, M.; Marks, T. J. "Multinuclear Olefin Polymerization Catalysts". Chemical Reviews 2011, 111, 2450.

         (21)  Huang, Y.; Qin, Y.; Zhou, Y.; Niu, H.; Yu, Z.-Z.; Dong, J.-Y. "Polypropylene/Graphene Oxide Nanocomposites Prepared by In Situ Ziegler−Natta Polymerization". Chemistry of Materials 2010, 22, 4096.

         (22)  Kang, J.; Yang, F.; Wu, T.; Li, H.; Cao, Y.; Xiang, M. "Polymerization control and fast characterization of the stereo-defect distribution of heterogeneous Ziegler–Natta isotactic polypropylene". European Polymer Journal 2012, 48, 425.

         (23)  Makio, H.; Terao, H.; Iwashita, A.; Fujita, T. "FI Catalysts for Olefin Polymerization—A Comprehensive Treatment". Chemical Reviews 2011, 111, 2363.

         (24)  Nikolaeva, M. I.; Mikenas, T. B.; Matsko, M. A.; Echevskaya, L. G.; Zakharov, V. A. "Heterogeneity of active sites of Ziegler-Natta catalysts: The effect of catalyst composition on the MWD of polyethylene". Journal of Applied Polymer Science 2010, 115, 2432.

         (25)  Takeuchi, D. "Recent progress in olefin polymerization catalyzed by transition metal complexes: new catalysts and new reactions". Dalton Transactions 2010, 39, 311.

         (26)  Elkin, T.; Kulkarni, N. V.; Tumanskii, B.; Botoshansky, M.; Shimon, L. J. W.; Eisen, M. S. "Synthesis and Structure of Group 4 Symmetric Amidinate Complexes and Their Reactivity in the Polymerization of α-Olefins". Organometallics 2013, 32, 6337.

         (27)  Gao, H.; Pan, J.; Guo, L.; Xiao, D.; Wu, Q. "Polymerization of 4-methyl-1-pentene catalyzed by α-diimine nickel catalysts: Living/controlled behavior, branch structure, and mechanism". Polymer 2011, 52, 130.

         (28)  Naga, N.; Yabe, T.; Sawaguchi, A.; Sone, M.; Noguchi, K.; Murase, S. "Liquid Crystalline Features in a Polyolefin of Poly(methylene-1,3-cyclopentane)". Macromolecules 2008, 41, 7448.

         (29)  Ricci, G.; Sommazzi, A.; Masi, F.; Ricci, M.; Boglia, A.; Leone, G. "Well-defined transition metal complexes with phosphorus and nitrogen ligands for 1,3-dienes polymerization". Coordination Chemistry Reviews 2010, 254, 661.

         (30)  Wang, L.; Cui, D.; Hou, Z.; Li, W.; Li, Y. "Highly Cis-1,4-Selective Living Polymerization of 1,3-Conjugated Dienes and Copolymerization with ε-Caprolactone by Bis(phosphino)carbazolide Rare-Earth-Metal Complexes". Organometallics 2011, 30, 760.

         (31)  Huber, J.; Mecking, S. "Aqueous Poly(arylacetylene) Dispersions". Macromolecules 2010, 43, 8718.

         (32)  Liu, J.; Lam, J. W. Y.; Tang, B. Z. "Acetylenic Polymers: Syntheses, Structures, and Functions". Chemical Reviews 2009, 109, 5799.

         (33)  Song, J.-A.; Park, S.; Kim, T.-S.; Choi, T.-L. "N-Containing 1,7-Octadiyne Derivatives for Living Cyclopolymerization Using Grubbs Catalysts". ACS Macro Letters 2014, 3, 795.

         (34)  Sugiyama, Y.-k.; Kato, R.; Sakurada, T.; Okamoto, S. "Chain-Growth Cycloaddition Polymerization via a Catalytic Alkyne [2 + 2 + 2] Cyclotrimerization Reaction and Its Application to One-Shot Spontaneous Block Copolymerization". J. Am. Chem. Soc. 2011, 133, 9712.

         (35)  Suginome, M.; Yamamoto, T.; Nagata, Y. "Poly(quinoxaline-2,3-diyl)s: A Fascinating Helical Macromolecular Scaffold for New Chiral Functions". Journal of Synthetic Organic Chemistry, Japan 2015, 73, 1141.

         (36)  Xue, Y.-X.; Chen, J.-L.; Jiang, Z.-Q.; Yu, Z.; Liu, N.; Yin, J.; Zhu, Y.-Y.; Wu, Z.-Q. "Living polymerization of arylisocyanide initiated by the phenylethynyl palladium (ii) complex". Polymer Chemistry 2014, 5, 6435.

         (37)  Xue, Y.-X.; Zhu, Y.-Y.; Gao, L.-M.; He, X.-Y.; Liu, N.; Zhang, W.-Y.; Yin, J.; Ding, Y.; Zhou, H.; Wu, Z.-Q. "Air-Stable (Phenylbuta-1,3-diynyl)palladium(II) Complexes: Highly Active Initiators for Living Polymerization of Isocyanides". J. Am. Chem. Soc. 2014, 136, 4706.

         (38)  Chen, Z.; Zuo, Y.; Li, X.-H.; Wang, H.; Zhao, B.; Shi, W.; Cheng, P. "Structure and luminescent property of novel 2D indium(III) and 1D cadmium(II) coordination polymers based on thiophene-2,5-dicarboxylic acid". Journal of Molecular Structure 2008, 888, 360.

         (39)  Yawer, M.; Kariem, M.; Sood, P.; Sheikh, H. N. "Lanthanide-based entangled coordination polymers connected by thiophene-2,5-dicarboxylate: solvothermal syntheses, crystal structures, luminescence and magnetic properties". CrystEngComm 2016.

         (40)  Zhan, C.-H.; Wang, F.; Kang, Y.; Zhang, J. "Lanthanide-Thiophene-2,5-dicarboxylate Frameworks: Ionothermal Synthesis, Helical Structures, Photoluminescent Properties, and Single-Crystal-to-Single-Crystal Guest Exchange". Inorganic Chemistry 2012, 51, 523.

         (41)  Boodhoo, K. V. K.; Dunk, W. A. E.; Vicevic, M.; Jachuck, R. J.; Sage, V.; Macquarrie, D. J.; Clark, J. H. "Classical cationic polymerization of styrene in a spinning disc reactor using silica-supported BF3 catalyst". Journal of Applied Polymer Science 2006, 101, 8.

         (42)  Bueno, C.; Cabral, V. F.; Cardozo-Filho, L.; Dias, M. L.; Antunes, O. A. C. "Cationic polymerization of styrene in scCO2 and [bmim][PF6]". The Journal of Supercritical Fluids 2009, 48, 183.

         (43)  Frolov, A. N.; Kostjuk, S. V.; Vasilenko, I. V.; Kaputsky, F. N. "Controlled cationic polymerization of styrene using AlCl3OBu2 as a coinitiator: Toward high molecular weight polystyrenes at elevated temperatures". Journal of Polymer Science Part A: Polymer Chemistry 2010, 48, 3736.

         (44)  Kuznetsov, D. M.; Tumanov, V. V.; Smit, W. A. "Cationic polymerization of styrenes under essentially neutral conditions". Journal of Polymer Research 2013, 20, 1.

         (45)  Ishido, Y.; Kanazawa, A.; Kanaoka, S.; Aoshima, S. "New Degradable Alternating Copolymers from Naturally Occurring Aldehydes: Well-Controlled Cationic Copolymerization and Complete Degradation". Macromolecules 2012, 45, 4060.

         (46)  Ishido, Y.; Kanazawa, A.; Kanaoka, S.; Aoshima, S. "Selectively degradable alternating copolymers of isobutyl vinyl ether and plant-derived aldehydes with acyclic side chains: Effects of side group structures on copolymerization behaviors". Journal of Polymer Science Part A: Polymer Chemistry 2013, 51, 4684.

         (47)  Ishido, Y.; Kanazawa, A.; Kanaoka, S.; Aoshima, S. "Chemically recyclable alternating copolymers with low polydispersity from conjugated/aromatic aldehydes and vinyl ethers: selective degradation to another monomer at ambient temperature". Polymer Chemistry 2014, 5, 43.

         (48)  Kanazawa, A.; Aoshima, S. "Exclusive One-Way Cycle Sequence Control in Cationic Terpolymerization of General-Purpose Monomers via Concurrent Vinyl-Addition, Ring-Opening, and Carbonyl-Addition Mechanisms". ACS Macro Letters 2015, 4, 783.

         (49)  Keitz, B. K.; Fedorov, A.; Grubbs, R. H. "Cis-Selective Ring-Opening Metathesis Polymerization with Ruthenium Catalysts".