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고분자신합성법
Hyperbranched polymer
Lipid and Protein
공업화학과/고분자재료연구실/석사2기
윤경준
Contents
Hyperbranched polymer
Introducton
definiton of terms
dendrimer와 hyperbranched polymer의 비교
history and advantage
Lipid
Introduction
Cross-linking polymerization
Polymerized liposome
Protein
General polymerization with ABx monomer
Nylon
Surface modification with protein
New approach with A2 and B3 monomer
1999. 12. 9
Hyperbranched Polymer
Definition of terms
Dendritic polymer, cascade polymer, starburst polymer, arborol
A highly branched polymer of precisely controlled branching structure produced by a
sequence of step-growth polymerization reaction steps.
– reference : Polymer Science Dictionary, Synthesis of polymer
Dendrimer 와 Hyperbranched Polymer의 비교
Dendrimer : 분자량 분포가 monodisperse하고 구형에 가까우며 최외각에 많은 작용기를 갖
는다. 합성에는 연속적인 반응과 정제과정이 수반되는 어려움이 있다.
Hyperbranched Polymer : 분자량 분포가 monodisperse하지는 않지만 globular 구조를 가지
며 외각에 많은 작용기들이 존재한다. ABx 형태의 단량체를 간편하게 “one-pot”중합
하여 제조 가능하다.
Linear polymers
Log[]
Hyperbranched
polymers
dendrimers
Log M
The intrinsic viscosity [] of polymers related to their molecular weight.
History
1952년 Flory의 예측
ABx형 단량체 중합 – 작용기 A : 1개, 작용기 B : n(x-1)+1개 (n=중합도)
낮은 물성으로 인하여 주목 받지 못함.
Advantage
Hyperbranched polymers might be a good alternative to dendrimers, as they can be produced on
a large scale at a reasonable cost.
Hyperbranched Aliphatic Polyesters
A. Hult, Macromolecules 1995, 28, 1698-1703
Objects
New hyperbranched polymer
Large scale production
Reaction scheme
Degree of Branching –
DB =
13C
NMR
dendritic units + terminal units
dendritic units + terminal units + linear units
For ideal dendritic substance, DB = 1
Possible repeating units in the
hyperbranched polyesters
Chemical shift for model compounds in acetone-d6
For theoritical generation 7
DB = 83%
Synthesis of Hyperbranched Aromatic polyamid
from Aromatic Diamines and Trimesic Acid – New approach
Macromolecules 1999, 32, 2061-2064
General method
ABx monomer : not commercially available
monomer 합성에 장시간 소요
New method
2 : 3 = feed ratio
A2 : commercially available for linear
+ condensation polymer
B3 :available as branching or cross linking
agent
Polymerization A2 and B3 in most case
Branching, cross-linking, cyclization
(insoluble in any organic solvents)
Consideration of reaction condition 
Hyperbranched polymer from A2 and B3
Reaction condition : polymerzation at 80C for
3 h with the total monomer concentration
of 0.21mol/L(3.3 wt%) in 80ml solvent
(NMP)  no gelation, soluble in organic
solvent
in 50ml solvent  gelation, insoluble in
organic solvent
Introduction
• Self-assembly : A process in which a Complex
hierarchical structure is established without external
intervention.
Lipid
:
비극성 유기용매의 추출에 의해
세포나 조직으로부터 분리되는 자연계에
존재하는 유기분자
종류 : 지방, 왁스
콜레스테롤, 스테로이드
Self assembling lipid
soap : 긴사슬 지방산의 sodium 혹은
potassium염의 혼합물
phospholipid : phophoglyceride, sphingolipid
Cross-Linking Polymerization in Two-Dimensional Assemblies
Macromolecules 1999, 32, 5519-5524
Macromolecues 1996, 29, 8321-8329
Introduction
Liposome화
monomeric amphiphilic lipid -------
polymerization ---- linear polymer or corsslinked polymer
Redox polymerizaton with K2S2O8 and
NaHSO3
Diret photoirradiation
Result
Depending on the number and location of
polymerizable groups per monomer
Various monomeric amphiphilic lipid
Stability of polymeric lipids
polymerization
Thermal AIBN polymerization
Cross-linked lipid more stable with surfactant
Emulsion – 액체 중에 그 액체와 혼합되지 않는 다른 액체의 미립자를 유화제의 도움을 받아
안정하게 분산시킨 것
Liposome – 인지질을 물에 현탁시킨 2분자막의 폐쇄 소포
Advantage – high biocompatibility
Drawback – stability
Application – drug delivery, biosensor etc.
Polymerized liposome
Langmuir 1998, 14, 1974-1976
Introduction
Advantage : physical stability,
durability during chemical modification
System
Uv light
Diacetylen functionalized lipid ------
Binding
Form conjugated system (blue)--------
Virus,toxin
Perturbation of  orbital overlap (red color)
protein : -amino acid residue
가 아미드결합된 거대 생체분자
단백질의 구조
• Primary structure : 아미노산 잔기의 결합서열
• Secondary structure
driving force : hydrogen bond 약 5kcal/mol
• Tertiary sturcture
driving force : 탄화수소 곁사슬의 소수성 상호작용
cyteine잔기사이에 이황화물 다리의 형성, hydrogen bond, salt bridge 등
피브로인의  병풍구조
케라틴의  나선형 구조
Aminoic acid
미오글로블린의 2차및 3차구조
Nylon –
polyamide, interchain hydrogen
bonding
Macromolecules 1998, 31, 8540-8548
Polymerization
• diacid + diamine
• amino acid
• ring opening of lactam
structure
(a) odd (b) even number of methylenes
in the diamine unit
Surface modification with protein
Langmuir 1997, 13, 6485-6490
Advantage : improve wettability and biocompatiblity
Method
Physical : hydrophobic or electrostatic interaction
reversible  buffer, detergent, other protein
Chemical : covalent bonding
irreversible, more popular