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									                   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?)。

• 本學期課程內容:
1. 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
                         Introduction –(2.18.2009)
•   Structure  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

    2010/2/4                    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)
    2010/2/4              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   油:大量生產,是Commodity Chemical (大宗化學品)。
效 能:汽車行駛能源,進氣閥,燃燒室,Emission。
添 加 劑: MTBE(7~15%),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 (de-hazer),染色劑,
       殺菌(Biocides)……等。

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
                    Key words (3-11-2009)

          What is ―patent‖? ---novelty and uses!
          Soft materials—shape changeable and reactive
           by shape changing; soft vs. hard materials
          Poly(isobutylene)-amine (PIB-) vs.
           Poly(ethylene)-imine (PEI) vs. PEG amine
          Synthesis and functions of PIB-ethylenediamine.
           Working principle—micelle in oil ?
          Hydroformylation or oxo process
          Polybutadiene

2010/2/4                  上課講義- 工業有機化學                  18
Example 3:    塑膠添加劑
一、抗氧化劑—purpose is to stop the hydrocarbon oxidation
  不飽和:3o > 2o > 1o ; 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 !
                                   (Butylated hydroxytoluene)

                 isobutylene




    What is the R group?

                                          Michael addition!




Butylated—alkylation via carbonium ion mechanism and by
Friedel 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?
PG+glycidyl alcohol




Glycidyl ether vs. glycidyl alcohol (glycidol) vs. glycerine




Multiple arms  geometric shape
Mw  property and function
In solvent, in bulk or in film---
tentacles or “polyvalent” functions
    Example 4: 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. Crystal or molecules or quantum dots
2. 366 nm irradiation  red emission
3. >450 nm  colorless
4. For 10,000 cycles of
   coloration/discoloration
5. The red is stable up to 120oC
   (can be erased with visible light)
1.   Multivalent cluster effect!
2.   Micelles –shape
3.   Sizes—molecular
4.   Role of polymer
     techniques
                    Key words (3-18-2009)

          Epoxy + acrylate
          Imine
          Antioxidant additives—free radical scavenger
           vs. free radical polymerization
          Phenol vs. P vs. S
          Polymers with multiple arms
          Polyvalent polymers – functions by geometric
           shape with multiple ―reactive‖ sites e.g., solid
           catalyst and biological function
          Micelle vs. Liposome

2010/2/4                   上課講義- 工業有機化學                       31
           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‖ (homework 1) 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 and confined structures)
   In connecting chemistry with engineering, material
    science, physics, biology, environmental (green
    chemistry), computer and etc.
        Inorganic nanomaterials in polymers
   奈米SiO2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SiO2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SiO2微粒和奈米TiO2 Al2O3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。

   Homework 2 –Can you design ―Novel‖‖ functional‖ material
    (according to the above ideas)?—use your creativity!
 Example 5: 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 carbon nanotubes
(CNT) 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: m2/g          Aspect ratio
Geometric shape
Functions and Applications : heat, physical properties,
  e.g., mp, heat distortion temp.
Quantum effect: (electron dot)
                : e.g., 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      1      10       102    103       104     105          106       107      108

               --------------
                                                                                               1 meter
Nanometers                NSP Nanodevices:
                                dendrimer

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

           Nano shells
                                                                        National Taiwan University
                                                              J.J.Lin     Polymer Institute
Does this molecule mean anything to you?
       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360oC,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)
                 Homework 3

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 (3-25-09)

  1.       Batch vs. continuous process
  2.       Micelle (critical micelle concentration CMC)
  3.       vs. (critical aggregation concentration CAC)
  4.       Bottom-up
  5.       Organic vs. nanoparticles and Soft vs. hard
           materials—nanomaterials
  6.       Nano scale in the Nature
  7.       ―Nano-process‖ of DNA duplication--
           kinetics
2010/2/4                 上課講義- 工業有機化學              47
    Functional Polymers (part 2) (3-09)

   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
             nitration!




Nylon 6,6!




PI!
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
modulus 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                   Supramolecules
(covalent bonds)             (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
                          (oral reports)
• Each team of 3 students
• Topics –review of 3 related papers and discuss with me to decide
the topics
• After midterm; one presentation of 20 min and followed by
discussion and comments
• Followed by quizzes
• Grade method– comprehensiveness, presentation, and
collaboration among the team members



   2010/2/4                上課講義- 工業有機化學                        54
        Morphology of Nanomaterials—
        in different shapes or dimensions




 rod- or fiber-like             Layered               Spherical

e.g., Carbon Nanotubes   e.g., montmorillonite, LDH    e.g., SiO2
                 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)
                 Key words (4-1-09)

  1.       Nanoparticles
  2.       Aspect ratio and three dimensional
  3.       Geometric shape and conformation
  4.       Solvating and solvation and solvophilic
  5.       ―Crown ether‖ concept




2010/2/4                 上課講義- 工業有機化學                62
                 (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 (SiO2) 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 MoS2 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)
                           (oral reports)
                           (home work)
                              (thesis)
•   What is known? What is novel? By literature citation !
•   What is your idea and why?
•   Research Proposal
•   Report
•   Project
•   Project Objective
•   Literature search and review



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   Functional Polymers—quiz-1 2009
   Elaborate or give answers to the following problems, terminologies and
   described phenomena (better by drawing their structures or using figure
   illustration to clarify your points)
   1. explain: (a) adding sodium hydroxide to a vial containing
   benzene/ether and stirring for a while; what will you observe? (b) then
   adding a ―crown ether‖ and stirring again; now what do you observe?
   2. draw a new structure of ―crown ether‖ and explain its function.
   3. a polymer material in bulk, in solution and as a thin film; what do they
   mean to you?
   4. entanglement vs. crystalline vs. amorphous
   5. quantum dot vs. CNT vs. clay
   6. photoresist
   7. PIB-amine vs. PEI
   8. What is the function that an ―aromatic amine‖ may have?
   9. batch vs. continuous process
   10. PLA vs. polycaprolactone (PCL)


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           Epoxy Chemistry and Nanotechnology

                    supplementary A




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     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


    C9H19             O(CH2CH2O)n H


    C14H29O(CH2CH2O)n H                                       (Low Mw)

                               CH3
    HO (CH2CH2O)c         (CH2CHO)a (CH2CH2O)b           H    (High Mw, <10,000 Mw)

Amphiphilic Copolymers:
   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 C60 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 C60 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++, Cuo/ Ago)

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
                                        micelles
amphiphilic peptides
  from marine bacteria




                                   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                                 N   N
            O                 O

        N                         N

                                  N            =            12Cu
        N

            O                 O
                N   N N   N




                                                             Chem. Eur. J, 3, 99 (1997)
                     Polymeric Electrolytes
                       (Salts Dissolved in Solid Polymers)
                     (Re-changeable Lithium Ion Batteries)


   Poly(ethylene oxide) (PEO) / lithium hexafluroarsenate (LiAsF6) = 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+     Li+      Li+
                                                  Nature, 398, 792 (1999)
   Cf. crown ether?
Vapor-phase assembly of multilayered structure
* 50 or more layers
* inter- planar π- stacking of aromatics
* Stable to heat up 300oC 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                                                NH       CH3
              O                       O                        O     NH
                                                                                   O
 O                   N       N                NH
         HN                      NH                    O
                                                                                   3
     O              O        O                     O
                                  O
                                          O

                  D = electron - donor                     A = electron-acceptor




                     A      D                 A        D       A          D
     -OOC



                         COO-                     COO-             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
  80oC (irreversible at RT)


                               JACS, 121, 2639 (1999)
   Room
Temperature   80OC
  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?




           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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