폴리올레핀 기반 블록 또는 그라프트 공중합체의 정밀 제조에 대한 고찰 = Study on the controlled preparation of polyolefin based block or graft copolymers

국문 초록 (Abstract)

폴리올레핀은 광범위한 분야에서 이용되는 범용성 고분자로 물성이 우수하고 가격경쟁력이 높기 때문에 오랜시간 동안 산업적 요구에 따라 발전하여 왔다. 그러나 폴리올레핀은 비극성 재료로서 다른 물질과의 상호 작용이 부족하기 때문에 그 용도가 제한되고 있다. 따라서 폴리올레핀 사슬에 극성기를 도입함으로써 그 응용 분야를 확장하기 위한 노력이 계속되고 있다. 폴리올레핀에 기능성을 부여하기 위하여 블록 공중합체 및 그라프트 공중합체로 대표되는 분절 공중합체를 합성할 수 있으며, 이러한 공중합체는 폴리올레핀 고유의 물성 손실을 최소화함과 동시에 기능성을 부여할 수 있다는 점에서 주목 받고 있다. 또한 리빙 라디칼 중합법을 이용하면 잘 제어된 구조와 조성을 가지는 공중합체를 제조할 수 있으며, 다양한 중합공정에 적용될 수 있다. 이에 따라, 본 리뷰에서는 리빙 라디칼 중합법을 이용한 폴리올레핀 기반 블록 또는 그라프트 공중합체의 제조 예들에 대하여 정리해 보았다.

다국어 초록 (Multilingual Abstract)

Polyolefin is one of the most important commodity polymers having excellent physical properties and cost competitiveness, which has continuously broadened their market in response to a heavy demand from industry. However, the lack of polarity in polyolefin has limited its applications, especially where interactions with other materials are important. In view of the above, the incorporation of polar functional groups in polyolefin has been widely attempted. Especially, the preparations of segmented modified polyolefin copolymers, such as block and graft copolymers have been extensively investigated, since the loss of the original properties of polyolefin can be minimized while the polar segments can endow interactions with other materials. Living radical polymerization (LRP) method can be one of the most attractive synthetic tools for the preparation of the modified polyolefin block or graft copolymers. In this review, progress on the preparation of the polyolefin based block or graft copolymers through LRP technique is briefly summarized.

참고문헌 (Reference)

1 Y. Miwa, "Well-defined polystyrene grafted to polypropylene backbone by “living” radical polymerization with TEMPO" 34 : 2089-, 2001

2 K. Yamamoto, "Well-defined poly(methyl methacrylate) grafted to polyethylene with reverse atom transfer radical polymerization initiated by peroxides" 44 : 7661-, 2003

3 N. Kawahara, "Synthetic method of polyethylene- poly(methylmethacrylate) (PE-PMMA) polymer hybrid via reversible addition-fragmentation chain transfer (RAFT) polymerization with functionalized polyethylene" 57 : 805-, 2006

4 R. G. Lopez, "Synthesis of well-defined polymer architectures by successive catalytic olefin polymerization and living/controlled polymerization reactions" 32 : 419-, 2007

5 C. Cao, "Synthesis of polypropylene graft copolymers by the combination of a polypropylene copolymer containing pendant vinylbenzene groups and atom transfer radical polymerization" 43 : 429-, 2004

6 M. A. J. Schellekens, "Synthesis of polyolefin block and graft copolymers" 40 : 167-, 2000

7 N. B. Bowden, "Synthesis of polyethylene graft block copolymers from styrene, butyl acrylate, and butadieneypropylene-poly(meth)acrylate block" 35 : 9246-, 2002

8 U. M. Stehling, "Synthesis of poly(olefin) graft copolymers by a combination of metallocene and Properties" 31 : 4396-, 1998

9 K. Matyjaszewski, "Synthesis of polcopolymers using metallocene catalyzed processes and subsequent atom transfer radical polymerization" 39 : 901-, 2002

10 A. Sen, "Synthesis of novel linear polyethene- based graft copolymers by atom transfer radical polymerization" 34 : 1529-, 2001

11 T. C. Chung, "Synthesis of functional polyolefin copolymers with graft and block structures" 27 : 39-, 2002

12 K. Zhang, "Synthesis of block copolymers of ethylene with styrene and n-butyl acrylate via a tandem strategy combining ethylene “living” polymerization catalyzed by a functionalized Pd-diimine catalyst with atom transfer radical polymerization" 41 : 640-, 2008

13 H. Kaneyoshi, "Synthesis of block and graft copolymers with linear polyethylene segments by combination of degenerative transfer coordination polymerization and atom transfer radical polymerization" 38 : 5425-, 2005

14 X. Wang, "Synthesis of EPDM-g-PMMA through atom transfer radical polymerization" 40 : 4515-, 1999

15 T. Matsugi, "Synthesis and morphology of polyethylene- block-poly(methyl methacrylate) through the combination of metallocene catalysis with living radical polymerization" 41 : 3965-, 2003

16 H. Kaneko, "Synthesis and characterization of polypropylene- based polymer hybrids linking poly(methyl methacrylate) and poly(2-hydroxyethyl methacrylate)" 49 : 4576-, 2008

17 H. Kaneko, "Synthesis and characterization of polypropylene- based block copolymers possessing polar segments via controlled radical polymerization" 47 : 812-, 2008

18 R. G. Lopez, "Synthesis and characterization of macroalkoxyamines based on polyethylene" 37 : 3540-, 2004

19 D. Sasaki, "Synthesis and applications of triblock and multiblock copolymers using telechelic oligopropylene" 49 : 4094-, 2008

20 J. M. Hwu, "Synthesis and application of functional polyethylene graft copolymers by atom transfer radical polymerization" 690 : 6300-, 2005

21 L. Barner, "Reversible addition–fragmentation chain-transfer graft polymerization of styrene: Solid phases for organic and peptide synthesis" 40 : 4180-, 2002

22 Y. Inoue, "Preparation of polyethylene block copolymers by a combination of postmetallocene catalysis of ethylene polymerization and atom transfer radical polymerization" 42 : 496-, 2003

23 S. C. Hong, "Preparation of Polyisobutene-graft-Poly(methyl methacrylate) and Polyisobutene-graft-Polystyrene with Different Compositions and Side Chain Architectures through Atom Transfer Radical Polymerization (ATRP)" 202 : 3392-, 2001

24 S. C. Hong, "Polyolefin graft copolymers via living polymerization techniques: Preparation of poly (n-butyl acrylate)-graft-polyethylene through the combination of Pd-mediated living olefin polymerization and atom transfer radical polymerization" 40 : 2736-, 2002

25 N. Kawahara, "Polymer Hybrids Based on Polyolefins– Syntheses, Structures, and Properties" 217 : 79-, 2008

26 T. Fonagy, "Polyisobutylenegraft- polystyrene by quasiliving atom transfer radical polymerization of styrene from poly (isobutylene-co-p-methylstyrene- co-p-bromomethylstyrene)" 19 : 479-, 1998

27 H. Yasuda, "Organo Transition Metal Initiated Living Polymerizations" 25 : 573-, 2000

28 T. Wannemacher, "Novel copolymers via nitroxide mediated controlled free radical polymerization of vinyl chloride" 202 : 11-, 2003

29 C. J. Hawker, "New Polymer Synthesis by Nitroxide Mediated Living Radical Polymerizations" 101 : 3661-, 2001

30 M. K. Georges, "Narrow molecular weight resins by a free-radical polymerization process" 26 : 2987-, 1993

31 M. Kamigaito, "Metal-catalyzed living radical polymerization" 101 : 3689-, 2001

32 K. Matyjaszewski, "Macromolecular engineering: From rational design through precise macromolecular synthesis and processing to targeted macroscopic material properties" 30 : 858-, 2005

33 N. Hadjichristidis, "Macromolecular architectures by living and controlled/living polymerizations" 31 : 1068-, 2006

34 M. Abbasian, "Living” radical graft polymerization of styrene to styrene butadiene rubber (SBR) with 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)" 15 : 606-, 2004

35 V. Percec, "Living" Radical Polymerization of Styrene Initiated by Arenesulfonyl Chlorides and CuI(bpy)nCl" 28 : 7970-, 1995

36 Y. Miwa, "Living radical graft polymerization of styrene to polypropylene with 2,2,6,6-tetramethylpiperidinyl-1-oxy" 32 : 8234-, 1999

37 K. Yamamoto, "Living radical graft polymerization of methyl methacrylate to polyethylene film with typical and reverse atom transfer radical polymerization" 40 : 3350-, 2002

38 J. Chiefari, "Living free-radical polymerization by reversible addition- fragmentation chain transfer: the RAFT process" 31 : 5559-, 1998

39 G. Moad, "Living Radical Polymerization by the RAFT Process-A Second Update" 62 : 1402-, 2009

40 S. D. Ittel, "Late-Metal Catalysts for Ethylene Homo- and Copolymerization" 100 : 1169-, 2000

41 K. Matyjaszewski, "Improvements in Atom or Group Transfer Radical Polymerization"

42 M. Baumert, "Highly branched polyethylene graft copolymers prepared by means of migratory insertion polymerization combined with TEMPO-mediated controlled radical polymerization" 21 : 271-, 2000

43 E. S. Park, "Grafting of polystyrene branches to polyethylene and polypropylene" 83 : 1103-, 2001

44 M. Roth, "Grafting of ethylenically unsaturated monomers onto polymers"

45 Y. Inoue, "Graft copolymers from linear polyethylene via atom transfer radical polymerization" 37 : 3651-, 2004

46 K. W. Doak, "Encyclopedia of Polymer Science and Engineering Vol. 6" John Wiley & Sons 386-, 1986

47 J. Y. Dong, "Design and synthesis of structurally well-defined functional polyolefins via transition metal-mediated olefin polymerization chemistry" 250 : 47-, 2006

48 L. S. Boffa, "Copolymerization of polar monomers with olefins using transition-metal complexes" 100 : 1479-, 2000

49 J. S. Wang, "Controlled/"living" radical polymerization. Atom transfer radical polymerization in the presence of transition-metal complexes" 117 : 5614-, 1995

50 H. D. Brouwer, "Controlled radical copolymerization of styrene and maleic anhydride and the synthesis of novel polyolefin-based block copolymers by reversible addition– fragmentation chain-transfer (RAFT) polymerization" 38 : 3596-, 2000

51 S. M. Desai, "Controlled grafting of N-isoproply acrylamide brushes onto self-standing isotactic polypropylene thin films: surface initiated atom transfer radical polymerization" 44 : 7645-, 2003

52 J. Bonilla-Cruz, "Controlled Grafting-From of Polystyrene on Polybutadiene: Mechanism and Spectroscopic Evidence of the Functionalization of Polybutadiene with 4-Oxo-TEMPO" 209 : 2268-, 2008

53 K. Zhang, "Chain Walking Ethylene Copolymerization with an ATRP Inimer for One-Pot Synthesis of Hyperbranched Polyethylenes Tethered with ATRP Initiating Sites" 28 : 2185-, 2007

54 R. G. Lopez, "Catalyzed chain growth of polyethylene on magnesium for the synthesis of macroalkoxyamines: Application to the production of block copolymers using controlled radical polymerization" 45 : 2705-, 2007

55 K. Matyjaszewski, "Atom Transfer Radical Polymerization" 101 : 2921-, 2001