功能性高分子

2009

(Functional Polymers)-2.18.2009

林江珍 • 功能性高分子課程為”高等高分子化學”之延伸。

(

故高等高分子化學為擋修課

?)

。 •

1.

本學期課程內容： 更進一步探討以高分子化學結構式及官能基

(functional groups)

表達高分子熱、光、電、機械及生化之性質。

2. Polymer Structures



Properties



Functions



Applications

• 講義內容：

attachment 1 (Lin

課程大綱：功能性高分子

)

• 上課形式：

1.

除了

lectures

外，鼓勵發問，討論。

2.

配合隨堂小考與課後

homework

。

3. Literature searching, reading and reporting

• • • • • • • • • •

Structure



Introduction –(2.18.2009) property



function



application Ethylene oxide vs. propylene oxide Ethylene vs. propylene Structure correctness Block copolymer or tri-block vs. homopolymer Hydrophilic vs. hydrophobic property Crystalline (e.g., PEG of 800 Mw) vs. amorphous Nanosize segregation in polymer domain (hard vs. soft segments) ---------------------------------------------------------------------- Industrial applications – such as polymer on silicate glass, film formation for optoelectronic devices e.g., epoxy-glass fiber lamination, adhesion and role-to-role manufacturing process

2020/4/30 上課講義 工業有機化學 2

化學”衍生”工業

( 化學工業

) (A)

大宗化學品

(Commodity Chemicals)—gasoline, pigment, paint…(formulation) (B)

高分子材料

(Polymers) —PE, PET fiber… (C)

特用化學品

(Specialty Chemicals) —dispersant..

(D)

生化材料

(Biotechnology and Biomedical Materials) —DNA carrier for therapy… (E)

光電材料

(Optoelectronics) —Lens (PMMA) (F)

微機電材料

(Micro-electro-materials) —Sensors, robots (integration)

Functional polymers (part 1)—

An introduction and examples of the “functional” polymers

Example: How much information hidden in this equation?

1. Reaction type? (step-growth or chain-growth…living?) 2. the way of drawing the scheme 3. s-BuLi 4. benzene vs. cyclohexane—solvent effect?

5. EO applications? 6. dibromide; selectivity ? (wrong structure!) 7. why to draw two types of reaction in one scheme (by abbreviation) 8. PS-b-PAN is still living…. 9. Structural meanings (functionalities?) 10. stoichiometric vs. catalytic 11. x and y (meaning of the ratio) 12. end group Br? 13. other critiques or mistakes (structural drawing) ? How about “functions”?



Tips for attending this class and doing research ( after learning technique —data, meanings, presentation)

Memorization vs. Reasoning (connection and convergent/divergent ways of thinking—logical approach)   (learning without thinking is useless; thinking without learning is unstable) The way of questioning, answering and reasoning --(to the point)---to be precise and to be concise (try to answer any question by less than three sentences) 2020/4/30 上課講義 工業有機化學 7

Polymers (basic concepts)

1. Polymer is a soft material (what is hard material?) 2. Random coils, worm-like, rod-like, lamellar, core-shell (micelle) … “importance of the geometric shape!”—functions 3. In solution (with solvent), in bulk, in film 4. solvent parameter—amphiphilic property e.g., PE, PS and Polyamide (structure and property?)

Polymeric Materials--issues

     

Chemicals (e.g., additive to polymers; monomers; inorganic; nanoscale particles….) Reactions —polymerization and modification Chemical structure and meanings Process (reaction types…) Performances (many different areas, including electronic conductance and light emitting…) New developments including concepts such as shape selective, supra-molecule, self-assembly, etc.

物 質 之 形 狀

1

、柔軟

(Soft) vs.

硬性

(hard) self-assembly : micelle vs. inorganic array 2

、球狀；層狀

(

雙層

)

，結晶狀

(

雪花

)

，

Carbon nanotube; C60; DNA (20 A), cyclodextrin (pore size 4.9 to 7.9 A), Cylinder; Linear… etc.

3

、

Entanglement vs. Crystalline Property vs. Amorphous 4

、多孔性：

0.5-2 µm diameter (

水滴

vs.

水分子

) 5

、奈米級：

m => mm => µm => nm => pico- => Femto-

材 料 之 物 理 性 質

1

、導電性：導電

Cu

金屬，導電有機高分子

vs. electrolyte 2

、透明性：玻璃、

PC

、

PMMA

、

EPOXY 3

、光反應：光阻劑

(photoresist; lithography

、光敏感劑

4

、相溶性：溶解

(e.g., NaOH

洗滌液

) (Solubility) 5

、相容性：

(Compatibility …biocompatibility) (1)

化學反應基

(2)

交聯反應

/

聚合反應

6

、

Dissolve vs. Solubilize (amphiphilic copolymer in one solvent or in two solvent system….micelle-like?) 7

、

polar vs. nonpolar vs. solvophilicity (solvation?)

物 質

(versatility in sizes)

1. Cyclodextrin-modified gold nanoparticles 2. Conjugated polymers as light emitting diodes 3. Fullerene-based surfactants 4. Clay and DNA 5. Graft copolymers 6. Light-induced amphiphilic surfaces 7. (Crown ethers and chelating sizes) vs. PEG

Specific Examples of Polymer Uses and Basic Concepts Involved examples for explaining the concepts of diversification of polymer applications

Example 1:

汽油添加劑

(

林江珍，界面科學會誌，

19, 3, 137, 1996)

汽 效 油：大量生產，是 添 加 劑：

Commodity Chemical (

能：汽車行駛能源，進氣閥，燃燒室，

MTBE(7~15%)

大宗化學品

Emission

，燃燒較完全，低污染， 。 抗震爆

(anti-knocking)

，抗氧化劑，抗腐蝕，

)

。 抗靜電劑，解乳化，去混濁劑 殺菌

(Biocides)……

等。

(de-hazer)

，染色劑， 特化

(Specialty Chemicals) = specialty polymers

？ 何為大宗化學品

s

？

Commodity….

Commodity Polymers vs. Specialty Polymers vs. High Performance Polymers vs. Functional Polymers

Patented structure (synthesis) Note: poly(isobutylene)-amine vs. poly(ethylene)imine or poly(ethyleneglycol)-amine *

小量生產，利用化工原理，界面原理，高分子引擎構造

*

同類新產品多，改變親油基、親水基、分子量

…

利益高，競爭大 •

200~300 ppm added in gasoline;

效益大，

Differentiate

汽油品牌 、品質

(

不投入，永遠落後

)

•

C&E News (2007)---Biomedical or Drug Development (3 billions research for one single drug)--- me-too vs. invention, research vs. marketing

Example 2: OXO Process (hydroformylation) for Specialty Chemicals: Polyurethane

，

Polycarbonate film

新聚合物，藥物控製釋放

US Patent 5,434,309(1995); 5,294,675(1994) to Monsanto

化學工業之架構

What is patent?—novelty and uses; claims

Example 3:

塑膠添加劑 一、抗氧化劑

—purpose is to stop the hydrocarbon oxidation

不飽和：

3 o > 2 o > 1 o ;

對氧不穩定。

(PE vs. PP vs. PS stability?) *

與塑膠之相容性

(compatibility)

。

*

減低揮發性及高溫加工性質。

*

降低

extractable

。

*FDA

食品包裝。

Regulation and FDA approval ?

用途：

Phenol (

酚系

) : PP, HDPE, LLDPE, LDPE, Styrenics, ABS, HIPS, Phenolic resin, PVC, SBS, Polybutadiene, EPDM

。

0.1~0.5wt% 0.02~0.1% 0.2%~1% Amine (

胺類

) (specialty

較少

) alkyl or aromatics

Anionic, cationic, free radical and catalyst

free radical generation—tertiary C oxidation and decomposition !

isobutylene (Butylated hydroxytoluene)

What is the R group?

Michael addition!

Butylated—alkylation via carbonium ion mechanism and by Fridel Craft Reaction with Lewis Acid catalyst—other reactions such as nonylphenol

AIBN: azo-di-isobutylnitrile

free radical generation—HC oxidation to peroxide and decomposition to free radical !

Secondary vs. Primary antioxidant

Imine formation and hydrogenation

Examples of functional polymers In the above three examples, how much do you know already?

Glycidyl ether vs. glycidyl alcohol vs. glycerine Multiple arms  Mw  geometric shape property and function In solvent, in bulk or in film-- tentacles or polyvalent functions

Key words-1

    

What is “patent”? ---novelty and uses!

Synthesis and functions of PIB-ethylenediamine. Working principle? Soft materials—shape changeable and reactive by shape changing Antioxidant additives—free radical scavenger vs. free radical polymerization Polyvalent polymers – functions by geometric shape with reactive sites e.g., solid catalyst and biological function

Example: Polymeric Materials and

前瞻化學材料

1. Diversity or Versatility (

多元化

) 2.

微小化

(

奈米化

) 3.

中心化

(Chemistry as “the central science”) 4. Polymers for electronic (e.g., LCD, color filter..) and biomedical (e.g., biocide, antimicrobial, drug delivery..) applications

1.

2.

3.

4.

5.

Crystal or molecules or quantum dots 366 nm irradiation



red emission >450 nm



colorless For 10,000 cycles of coloration/discoloration The red is stable up to 120 o C (can be erased with visible light)

1.

2.

3.

4.

Multivalent cluster effect!

Micelles –shape Sizes—molecular Role of polymer techniques

The Revolution in Chemistry (and the trend to nano scale)

     

Converting naturally abundant substances into chemically useful building blocks (e.g., chitosan?) Developing the art of reaction or process without solvents--(ionic liquids in the prior arts?) Understanding the properties of compounds of intermediate (1-100 nm) size--nanotechnology Creating molecules that self-assembling—micelles Mastering the chemistry of caged spaces that response to the introduction of chemical, magnetic or electric field in entrapped an appropriate host (e.g., hybrids and organoclays) In connecting chemistry with engineering, material science, physics, biology, environmental (green chemistry), computer and etc.

Inorganic nanomaterials in polymers

 奈米

SiO 2

微粒是三維

(?)

鏈狀結構，將其均勻地散在橡膠大分子中會與之結 合成為立體網狀結構，達到改善橡膠製品強度、彈性和耐磨等性能。  奈米

SiO 2

微粒對波長

499nm

以內的紫外線發射率達

70%~80%

，所以也可 以提高橡膠的 抗老化 性能。

(conventional antioxidants)



298~400nm

波段的紫外線能使高分子材料的分子鏈斷裂，使其出現老化。 奈米

SiO 2

微粒和奈米

TiO 2 Al 2 O 3

和

ZnO

微粒可以吸收大量的紫外線。  奈米

ZnO

微粒或奈米金屬微粒添加到塑料中，可以得到 抗靜電 的塑料。 

Can you design “Novel” functional material (according to the above ideas)?— (homework-1)

Example 4: Nanotechnology (new trend) According to the IUPAC definition porous materials can be classified into three groups. Microporous: pore diameters less than 20 A; Mesoporous: from 20-500 A Macroporous: larger than 500 A Microporous materials include amorphous silica to crystalline zeolites (aluminosilicates) Nano-scale : 1-100 nanometer.

Some examples of nanoscale materials

1. A human hair has width of 1 micro-meter which is 1000 nanometers. (conventional materials!!!) 2. Micelle is a nano-particle, which can be 20 nm.

3. Microelectronics rests on 100 nanometers or less

Fabrication: top-down and bottom-up

1. Patterns generated on a larger scale and reduce to smaller dimension. 2. Bottom-up (easily to be 2-10 nm) Two prominent methods are nanotubes and quantum dots. Quantum dots are crystals containing only a few hundred atoms. The electrons are confined to widely separated energy levels, the dot emits one wavelength of light when it is excited.

Soft and Hard Materials



Hard materials have a controllable shape such as zeolite, clay, buckyball, crystalline polymers, etc.



Soft materials are flexible, most time, they are in sphere particle shape, such as amorphous polymer molecules (random coil); micelle; polymer crosslinked particles…..

“Nano” Definition

One of three dimensions in 1~100 nm (nm = 10 -9 m) Area/weight: m 2 /g Aspect ratio Geometric shape Functions and Applications : heat, physical properties, eg mp, heat distortion temp. Quantum effect: (electron dot) : eg. Color, electric conductivity (bulk vs. surface atoms)

Nanotechnology and Polymers

     

Nano-materials, -technology and –science (examples—conducting polymer) e.g., surface active agent, micelle ….. Lotus effect (phenomenon, principle and applications) EMI (electromagnetic shielding insulation) Polymer: blend, crystalline material… Inorganic/polymer composites Inorganics (powder…..) Biomaterials (DNA, protein,….); Biosenser

Nanomaterials—meanings



Miniaturize (nanoscale size)



Surface



Shape



Functions (applications—novelty)



Diversity (including Biomaterials)

“There is plenty of room at the bottom “

bottom-up vs. top-down



1959

年，

(Richard Feynman)

，  自然界中的血紅蛋白分子及直徑僅為幾個奈 米，病毒尺寸一般都在數十奈米左右。  跳蚤可以輕鬆躍起數百倍於自己身長的高度； 螞蟻能夠撼動幾十倍小於自己體重的物體； 蜜蜂煽動翅膀的頻率可以高達每秒上百次。  蜘蛛吐出又韌又黏的絲。

(observing the process!!)

Size Comparison of Nanomaterials

water Glucose Antibody Virus Bacteria Cancer cell A period Tennis ball 10 -1

Nanometers

1 10 10 2 10 3 ------------- NSP

Nanodevices:

dendrimer 10 4 quantum dots Nano tubes 10 5 10 6 10 7

Nano Silicate Platelet (NSP): Size, Geometric and Charge Interactions

10 8 1 meter Nano shells

National Taiwan University J.J.Lin Polymer Institute

http://pubs.acs.org/email/cen/html/031706212813.html

Homework 2

With the concepts of “soft/hard” material and “nanosize effect” in mind, can you derive an equation to correlate “surface to dimension” of a particle (particle size?), a tube (cross-section and length?) and a platelet (thickness and disc shape?), assuming three materials have an identical weight ?

Key words

1. Micelle (critical micelle concentration CMC) vs. (critical aggregation concentration CAC) 2. Bottom-up 3. Soft-hard materials 4. Nano scale in the Nature

Is DNA a soft or hard material ?



DNA

分子的結構和複製過程： 

1953

年

Watson

，

Crick. DNA

分子的直徑為

2nm,

雙螺旋的螺距為

3.4nm

。 

10

個鹼基對共旋轉

360 o C

，正好為一個螺距。



1982

年，

IBN

掃描隧道顯微鏡

(Scanning Tunneling Microscope, STM)



1986

年，原子顯微鏡

(Atomic Force Microscopy, AFM)



STM

和

AFM

後來統稱為

SPM (Scanning Probe Microscopy)

Functional Polymers (part 2) (3-19-08)



Properties vs. structures ? (e.g., polar vs nonpolar) Applications or Functions (CNT conductivity -> EMI)



From primary to secondary structure….



From one-dimensional to two-dimensional films



Self-assembly to supramolecules from copolymers

Nylon 6,6! PI! nitration!

All the sulfonated samples having high-molecular-weights (Mn, 74,100–109,500) were soluble in some polar aprotic solvents such as DMF, DMSO and DMAc, and they could be easily formed into tough and flexible films via solution casting. (why film?) The films presented good thermal stabilities (T5% > 453 C), and mechanical properties (high storage moduli and glass-transition temperatures (Tg > 220 C), as well as tensile strengths of about 95 MPa) and swelling degrees lower than 12%. (cf. methyl cellulose)

Chemistry (beyond covalent bonding and structure) Molecules (covalent bonds) Supramolecules (non-covalent bonds) Geometric/Physical Functions (e.g. 1. Protein tertiary structure 2. Nano-materials 3. swelling –crosslinking network )

Serendipity!!! Surfactant? Water/oil? Water/ethanol? Water on glass? Dispersion (RBG,CB or sand) vs. solution? On water surface? Surface or interfacial tension energy? Anti-surfactant?

“Crown Ether”: chelating, guest/host interaction---geometric effect

Morphology of Nanomaterials— in different shapes or dimensions

rod- or fiber-like Layered e.g., Carbon Nanotubes e.g., montmorillonite, LDH Spherical e.g., SiO 2

Polymers

bulk (crystalline vs. amorphous) solution (solubility, coil and amphiphilic) film (OLED, color filter from bulk polymers ?

and nanoscale manipulation ?) self-assembly into three dimensional materials (self-assembling process or kinetics; and self-assembled arrays or supramolecules or ordered aggregates)

Block Copolymers as Surfactants and their Applications (amphiphilic!)



Diblock, triblock and multiple block (such as octa block)



Poly(styrene)-b-poly(butadiene)-b-poly(styrene)



Graft copolymers—PP-g-MA (how to make it?)



Note: synthetic approach vs. structural design—a. EG-initiated EO/PO block vs. glycerin-initiated EO/PO vs. SBS terminated with CBr4

Polymeric Nanoparticles

(Acc, Chem. Res. 2001, 34, 249)



Concept : e.g., emulsion polymerization of polystyrene with anionic surfactant, sodium dodecyl sulfate (1.8 w%), to form up to 40 w% PS (as low as 60 nm nanoparticle) vs.



polymeric copolymer as surfactant. That is, non-extractable surfactant. (surfactants as “templates”; polymers are nano-particles..)

Polymeric Nanoparticles (cont’d)



Polymeric nanoparticles: block copolymers and ionomers can self-assemble in a selective solvent to be nanoparticles—amphiphilic copolymers--- at least two different blocks—solvation differently by a solvent. (solvophilic or solvent-selective!)



Size: 100 to 1000 nm; current technology: it is hard to achieve 10-100 nm and stable in water.



Cf. inorganic nanoparticles– 5-100 nm (but it is challenging to have 5-10 nm metal particles with good dispersity) (nanotechnology)

Polymers are soft particles while metal (and metal oxide) are hard ones



Degree of flexibility



Different shapes or conformations (conformational entropy)



Approximately spherical coil shape



The conformation entropy gives the coil a certain elastic resistance to deformation such as squeezing and stretching. (three dimensional materials…)

Amphiphilic Block ABA Copolymers as Polymeric Surfactants



Summary: 1. Non-ionic and cationic structures—amphoteric 2. Temperature-sensitive (up to 39 C; due to biological functions ) 3. pH-sensitive (from 10 to 5 to 2) 4. Micellar self-assembly and phase inversion 5. Self-assembly in bulk (phase separation as in SBS)

(3-26-08) – review 1. The aggregation changes in different environments 2. Non-covalent bonding forces 3. geometric shapes and for templates 4. hierarchical transformation or kinetic vs. thermodynamic changes

Polymer for Self-assembly (secondary and tertiary structures) (bulk and film; from one-dimensional to two-dimension) (what is “three-dimensional” ?)

Ultra-thin organic films vs. Conventional coating a. wet process Self-assembly monolayer (SAM) Langmuir-Blodgett (LB) Synthetic lipid bimolecular layer Electrodeposition Layer-by-layer b. dry process (vacuum) vapor deposition (by sublimation or bulk material ablation) (note: logo!)

Ultra-thin organic films



Organic electroluminescent (OEL) or light emitting diodes (LED) display device using vacuum deposited thin films (about 50 nm thick) have been achieved.



Organic Light Emitting Diodes (OLED)



PLED (polymer LED)

The chemical structures of 8-hydroxyquinoline derivative-metal complexes

The chemical structure of BeBq2, ZnBq2 and ZnAC2

Chemical structure of ZnBTZ

Chemical structure of azomethine-metal complexes (imine structure)

The chemical structure of Zn-porphyrin

The chemical structure of Eu(TTA) 3 (phen)

Polymer LED

Science, 285 , 233 (1999) Dispersing 5-nm particles of silica (SiO 2 ) in poly(p-phenylenevinylene) (PPV), whose refractive index be tailored from 1.6 to 2.7

Optoelectronics



Organic Light-emitting Diode (OLED)

) 4 C

Bright Blue Light JACS 120, 2987 (1998)

OLED Red Light

OLED Green Light

OLED Blue Light

3-Layer Device

Key words

1. LED



OLED



PLED (polymer light emitting diodes) 2. Thin film process 3. Nanoparticles (micelle-like, shape changing, responsible to forces, temp, pH, light, magnetic….



functions)

Molecular Orientation of ClAl Phthalocyanine in Vapor Deposition Process on MoS 2 Substrate

Dendrimers with Self Assembling Property and Their Superstructures

Two Dimensional Polymer System Using Xanthate Modified Dendrimer SAMs of inorganic-organic two-layer polymers, which are laminar metal hydroxides with mercapto groups made by sol-gel reaction.

Chelating or tethering or non-covalent bonding to “fix” the geometric shapes

Summary 1: Polymer chemistry is the “fundamental” knowledge

       

Fundamentals: polymer synthesis, structure and property 5 noncovalent bonding forces (science) Supramolecule and self-assembly (technology) Biopolymers (naturally occurring) Hydrophilic polymers (polyacrylic acid, PVP etc) vs. hydrophobic polymers EO-PO copolymers is one of important classes molecular architectures by precision polymerization Others (1. epoxy for advanced materials – attachment A)

Epoxy Chemistry and Nanotechnology supplementary A

2020/4/30 上課講義 工業有機化學 85

Biopolymers (or biological macromolecules) (in Nature, there are materials in nanoscale– size and biological process– through self-assembling Primary structure (covalent bonds) Secondary and tertiary structure (noncovalent bonds) 1. The primary structure of many biopolymers (e.g., sugar, protein, DNA, etc.) is linearly architected. 2. The complex and specific behaviors behind the simple structure are caused by their secondary and tertiary structures (e.g., biological functions of a protein)

Surface Active Agents: Anionic, Cationic, Amphoteric and Nonionic C 9 H 19 O(CH 2 CH 2 O) n H HO (CH 2 CH 2 O) c CH 3 (CH 2 CHO) a (CH 2 CH 2 O) b Amphiphilic Copolymers: H (Low Mw) (High Mw, <10,000 Mw) Consisting of distinct polar/non-polar blocks or blocks with different dissolving properties (or good solvent/poor solvent properties); capable of forming non-covalent bonds: (a) hydrogen bonding (b)



-



interaction; alkyl hydrophobic interaction (c) ionic charge interactions (d) van der Waals forces—e.g., nanoparticle aggregation

Chemical structure of a C 60 molecule. With 60 atoms the molecule can be regarded as a “mini-solid”. The molecule has a diameter of 7.1 A

。

Two-dimensional view of a fullerene crystal. The C 60 molecules in interact only by weak van der Waals forces.

特性：

(1)

水溶及油溶兩大類

(2)

界面活性

(Surfactancy):

液

/

液、液

/

固、固

/

固

(3)

分散性

(Pigments, Nano-scale clays, Inorganic Mg ++ /Ca ++ , Cu o / Ag o )

工業應用：

(1)

高分子型界面活性劑

(emulsification, solubilization) (2)Pigment Dispersants for Color filter (3)

抗污劑，抗氧化劑

(4)

水性化

(water-borne) (5)

高分子相容劑

(compatibilizer) (6)

抗靜電劑

(7)pH Sensitive

藥物釋放

(8) OLED/polymers (8) Nano-scale materials

Emulsion of hexane/water by Cm-BO at 1600 Mw at 1.5g/4.0g/4.0g (magnification, 500x)

Emulsion by SEBS-g-MA/ED6000 (3.75% in toluene) in Toluene/Water (500 X)

Structures beyond the primary

Self-assembly, Self-organization, Self-synthesis Self-assembly involves the aggregation of molecules and macromolecules to thermodynamically stable structures which are held together by weak concovalent interactions, including hydrogen bonding, pei-pei interaction, electrostatic and van der Waals forces, and hydrophobic and hydrophilic interactions. The self-assembly process offers considerable advantages over stepwise bond formation in the construction of large supramolecular assembles.



Self-organization is a higher order of self assembly in which the non-covalent interactions usually more specific and more directional.



Self-synthesis embraces not only self-assembly and self-organization, but also self-replication and template-type polymerization or autocatalysis. (mimicking to the Nature)

Key words

   

Dentritic shape—Dendrimer having different hemispheres and surfactant properties Surfactants—self-assembling properties which have different shape of arrays (highly ordered structures) (micelle-like, shape-changing, responsible to forces, temp, pH, light, magnetic, functions) Thiol compounds—what is the function?

Science, 287, 1245 (2000) Self-assembling amphiphilic peptides from marine bacteria micelles Spherical particles at 140 - 180 nm Biological function can be derived from a self assembly !

= Fe(III)-Marinobactins

ABA Triblock Copolymers— first example of self-assembly Shell Kraton-D (SBS) Thermoplastic Elastomer £k-£k stacking cross-linking (rubbery) thermal reversible linear (Microphase separation) ABA Covalent vulcanization vs. non-covalent self-assembly Telechelic polymer : reactive end groups e.g. , adipic acid + 1,6-hexanediamine at controlled stoichiometric

Supramolecules via metal coordination

（

C&E News, June 8, 1998

） 

designing and creating molecules to spontaneously organize themselves into larger supramolecular assemblies (by H-bonding or metal coordination)

N N O N N O N N N N O N N N N O

= 12Cu Chem. Eur. J, 3, 99 (1997)

Polymeric Electrolytes

(Salts Dissolved in Solid Polymers) (Re-changeable Lithium Ion Batteries)



Poly(ethylene oxide) (PEO) / lithium hexafluroarsenate (LiAsF 6 ) = 6 : 1



The duel polymer chains interlock to form nonhelical cylinders. The lithium ions line up in rows within the polymer cylinders, far removed from the anions that stack up outside, for ions free to zip about.



cf . Helical or a stretched zig-zag conformation . Li + Li + Li + Li +



Cf. crown ether?

Li + Li + Nature, 398, 792 (1999)

Vapor-phase assembly of multilayered structure

* 50 or more layers * inter- planar π- stacking of aromatics * Stable to heat up 300 o C and to most organic solvents and acids * Has fabricated organic LEDs as tiny as 3 nm thick for a four layer device C&E News, April 13 (1998) P.44

An Amphiphilic Copolymer that Undergoes Folding and Irreversible Conformational Change

O O O HN O O O O N N NH O O O O

D = electron - donor

NH O O O NH NH O 3 CH 3

A = electron-acceptor OOC A D COO A D A COO D COO -

An Amphiphilic Copolymer that Undergoes Folding and Irreversible Conformational Change (Cont’d) * a deep-red solution in water at RT; Folding inter-molecularly * becoming a pale-pink gel (tangled aggregation) at 80 o C (irreversible at RT) JACS, 121, 2639 (1999)

Room Temperature 80 O C

Intermolecular link stabilizes self-assembled peptide cylinder C&E News, Jan.15 (1996), p.18

Self-assembly into nanotubes (13 A in diameter) which aggregate into 200-300 microns

Cy = cyclohexyl

Cell-surface Engineering



Carbohydrate–based drug delivery



Modification of tumor cells to increase the drug uptakes (C&E New, May 5, 1997) (C&E New, Feb 2, 1998 )

Synthetic polymers recognize all four base pairs in DNA (Nature, 391, 468, 1998)



Polyamide consisting imidazole, hydroxy pyrrole and pyrrole units



Wraps around segment of double – strained DNA, through hydrogen – bonding to thymine (T), guamine (G), adenine (A)

Planar-support solid-phase synthetic technique C&E News, July 3 (2000), p. 26 Biopolymers, 47, 397 (1998) Chemical reactions are carried out in small spots on functionalized planar supports made of paper, cloth, or polymer.

Review



Polymers vs. Copolymers



Interacting with nanoscale inorganics



Secondary structure—self-assembly



Two-dimensional devices—film



Property vs. Applications

Required Reading: “Advanced functional polymer membranes” by Mathias Ulbricht * Polymer 47 (2006) 2217–2262 (www.elsevier.com/locate/polymer) Oral reports: 1. Synthesis and chemical structures 2. Experimental procedures—how to do the experiments 3. Property/Performance 4. Critiques and comments: Meaning of data, significance, uniqueness and contribution to this area of research 5. Powerpoint presentation—how to prepare

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Suggested Topics for Oral Reports (2008)

1. sol-gel reactions and polymers (2 students) 2. Free-radical living polymerization—process or polymer structure or applications (3-4) 3. AgNP, AuNP, Fe3O4, ….nanoparticles— synthesis/function/application----biomedical and magnetic property, etc. 4. self-assembly (and nanoarrays) (2) 5. amphiphilic copolymers (2) 6. self-assembly, self-organization and self-synthesis 7. polymeric electrolytes (new development) (1)

Literature example 1: Discussion on (1) homo-polymers vs. copolymers (2) Starting material sources (3) extension or prediction: amine functionality and how to make it and property different pH sensitive (4) carboxylic acid ?

(5) New knowledge and new proposal—average or innovative proposal?

2020/4/30

By varying the polymer structure, its function is changed.

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Unique Properties

Among these polymers, one of the most representative examples is poly(

N

-isopropylacrylamide), which is hydrophilic and exists in a random coil in water below 31 ° C. The copolymer corresponds to a lower critical solution temperature (LCST). Above the LCST, it becomes hydrophobic and changes its conformation from a

random coil to a globule

, then aggregates due to the hydrophobic interaction among the isopropyl groups. It has potential uses to immobilize bioactive molecules, such as peptides and proteins. The polymer is temperature-responsive but unaffected by the pH.

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Quiz 1: redraw the following “reaction scheme”!

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Quiz 2: draw the synthetic “schemes” 1. Poly(styrene)-b-poly(butadiene)-b-poly(styrene)— a triblock copolymer 2. EG-initiated EO/PO triblock copolymer

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Homework



Do a literature search or use your imagination to illustrate an example of “dispersion”. [hint: what is being dispersed? in what medium? by what dispersant (a copolymer)?



And explain the principle and uses.

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Key words

1. Sulfonation: –SO3H in imidazole- linking polymer film 2. Crown ether: Planar ? Crystalline ? Solubility (insoluble in methanol but soluble in NaOH/methanol)? Geometric size? Metal complex (soft+hard material)



functions (i.e., metal salt into organic matrix! Interface!) 3. Surpamolecules by self-assembly—anti surfactant ?

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Quiz 1 ( )

1. what is “anti-surfactant”?

2. elaborate the meanings of “18-crown-6” structure 3. elaborate the meanings of “PIB-ethylene-diamine” structure.

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Key words 2

 

Oxo process; hydroformylation; synthesis gas Anti-oxidant Mechanism vs. olefin polymerization Amine synthesis—aromatic and aliphatic amine (Isophorone diamine?)

  

Polyvalent interaction for drug design New Chemical Developments (

前瞻化學材料

?) Nanoscale—meaning

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