고분자개론 1장

2024-Spring
Introduction to Polymers
Chapter 1. Concepts and Nomenclature
Department of Energy Science and Engineering
Chiyoung Park
parkcy@dgist.ac.kr
E6-512
water traped .
tail
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Scientific Reports 2020, 10, 12867
Radical
Key Concepts
Brief History
Definition
Nomenclature
Skeletal structure
> 1 개의 repeat Unit
Homopolymer
x
=
Copolymer
…
r> Mixed repeat unit .
Classification
Molar mass & Degree of polymerization
Differences between polymer and small molecules
mmmm
%
Brief History
Vulcanization ,
Q
Brief History
1
항성고무
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~N
중합이후에도 <
추가적 중합가능,
1.1. The Origins of Polymer Science & The Polymer Industry
IN
- trate
,
plasticizer -
가소제
인력 감소 ↓ ~
위연성
( 약
Macromolecular Concept
Leading organic chemists such as Emil Fischer and Heinrich Wieland believed that
the measured high molecular weights were only apparent values caused by the aggregation of
small molecules into colloids
Heinrich Otto Wieland H. Staudinger

(1877-1957) (1881-1965)
1927, Nobel Prize 1953, Noble Prize
https://onlinelibrary.wiley.com/doi/epdf/10.1002/anie.200330070
초분자 중합처 ( →
Noucovalent bond로 Interactiol
Self-Assembly & Supramolecular Polymers

Polymer Hypothesis : Polyelectrolytes
@
@
e Or xamonium eatoon
In the 1930s, Marvel and coworkers uncovered some of the earliest evidence to support Staudinger’s revelatory
“Polymer Hypothesis” in their investigation of halogenated alkyl dimethylamines. The authors discovered that during
@
self-quaternarization, both ionic and covalently bonded halides were detected in the products, a finding that
confirmed the formation of linear polymers instead of the previously proposed cyclic dimers.
[1] E.R. Littmann, C.S. Marvel, J. Am. Chem. Soc, 1930, 52, 287-294.
[2] C.F. Gibbs, E.R. Littmann, C.S. Marvel, J. Am. Chem. Soc., 1933, 55, 753-757.
[3] M.R. Lehman, C.D. Thompson, C.S. Marvel, J. Am. Chem. Soc., 1933, 55, 1977-1981.
[4] G. W. Coates et al., Alkaline-stable Anion Exchange Membranes: A Review of Synthetic Approaches. Prog. Polym. Sci.
2020, 100, 101177.
Herman Staudinger
Paul Flory
1953 : for his 1974 : for his fundamental
discoveries in the field achievements, both
of macromolecular 1963: for their discoveries in the field of the theoretical and experimental,
chemistry chemistry and technology of high polymers in the physical chemistry of
the macromolecules
2000 : Conducting polymers
1991: for discovering that methods

developed for studying order phenomena
2005 : for the development of the
in simple systems can be generalized to
metathesis method in organic synthesis
more complex forms of matter, in
particular to liquid crystals and polymers
Cold Drawn
1.2. Basic Definition
Polymer: a substance composed of molecules which have long sequences of
one or more species of atoms or groups of atoms linked to each other by
primary, usually covalent bonds.
) 분자량 A 귀칙성시
N
, *
*
Macromolecule
 Polymer = poly (many) + mer (part)
 Macromolecule = large molecule Polymer
x 최릭성
~~
있어야
( monomer) ,
@
 Monomer = one part (unit)
 Dimer = two units = two monomers connected
Monomer, dimer, trimer, tetramer, pentamer…. n mer
@
 Oligomer = a few parts (n < 100)
T
xioo
Nomenclature :
Pole + monomer
)
1) Nomenclature Based on Source (IUPAC)

: The most simple and commonly used nomenclature system is probably that based on the
source of the polymer. Polymers are named by adding the name of the monomer onto the
prefix ‘‘poly’’ without a space or hyphen.
Ethylene  Polyethylene
Acetaldehyde  Polyacetaldehyde
3-methyl-1-pentene  poly(3-methyl-1-pentene)
Vinyl chloride  Poly(vinyl chloride) Monomer = substituted
Propylene oxide  Poly(propylene oxide) parent name or a
Chlorotrifluoroethylene  Poly(chlorotrifluoroethylene) multiworded name
E-caprolactam  Poly(E-caprolactam)
Nomenclature
2) Nomenclature Based on Structure (Non-IUPAC)
: A number of the more common condensation polymers synthesized from two different
monomers have been named by a semisystematic, structure-based nomenclature system
other than the more recent IUPAC system. The name of the polymer is obtained by
following the prefix poly without a space or hyphen with parentheses enclosing the name of
the structural grouping attached to the parent compound. The parent compound is the
particular member of the class of the polymer—the particular ester, amide, urethane, and
so on.
amide PolHamides
요 e
hexametuylene diamide Sebacic acidd
.
Poly(hexamethylene sebacamide) ~
Ethylen glyo 이 ( Ea ) * 조
.
Poly(ethylene terephthalate)
r
…
Carbamate
0
Poly(trimethylene ethyleneurethane)
Classification of Polymers
1. According to the chemical structure
-개의 repeatiy unit
폴리며
V
Polymer 째 이상
2
repeativy unit
Homopolymer Copolymer
“Depending on whether there is

one or more repeating units
constituting the polymer”
ABAB …
Random Copolymer Alternating Copolymer
Block Copolymer Graft Copolymer

AAAABBBBAAAA …
- AAAAAAAA …
IBBBBL
1.2.1. Skeletal structure
O O
e ~
Definition: Star Polymer & Dendrimer
Star polymer  macromolecules & polymers:
공통 extremely large molecules with
ex) tri-star polymer high molecular weight
차이  polymers :
repeating units from polymerization
 macromolecules:
polymerized and non-polymerized
molecules
Dendrimer: Tree-like macromolecules by iterative synthesis

Starburst dendrimer: by divergent synthesis
1.2.2. Homopolymers
<Homopolymer Example>
 -[A]n-
"
CH CH
2 2
Polyethylene Homopolymer Polyethylene Repeating Unit
( )
Poly(ethylene oxide) Homopolymer Poly(ethylene oxide) Repeating Unit
1.2.2. Homopolymers: Nomenclature
 General methods
1) Structural method: poly + repeating unit (for condensation polymers)
poly (ethylene terephthalate)
two or more words
poly (ethylene terephthalate)
in brackets
vs. polyethylene
2) Source method: poly + monomer (for addition polymers) one word
polyethylene
3) IUPAC
- Poly(chemical structure of repeating unit)
Poly(methylene) Poly(oxyethylene oxyterephthaloyl)
-[따랑
4) Commercial: Nylon, Teflon, etc.
5) Abbreviations: PE, PP, PVC, PS, PMMA, PET, PC, PPO, etc.
1.2.2. Homopolymers
1.2.2. Homopolymers
1.2.3. Copolymers
Copolymer
- 2 or more different repeat units linked by
covalent in a chain
<Copolymer Example>
<Random Copolymer> <Graft Copolymer>
• Different monomers randomly bonded
<Block Copolymer>
• Different monomers form blocks
<Alternating Copolymer> • Block attached to the side branch
• Different monomers alternately bonded

1.2.3. Copolymers: Nomenclature
Poly(methyl methacrylate)-b-poly(n-butyl acrylate)
ㅡ ㅡ
ㅡ
…
Poly(methyl methacrylate–co–n-butyl methacrylate)-b-

poly(n-butyl acrylate)
1.2.4. Classification of Polymers
Popular classification
열가소성수지 열경화성수지
사
m m
<Linear Polymer> <Branched Polymer> <Crosslinked Polymer>
Form
<HDPE>
과 …
<LDPE> <Crosslinked Polymer>
…
Example
Characteristic It is well soluble in solvents and softens It does not dissolve in a solvent,
or melts when heated. and only swelling occurs.
~
?
Thermoplastic Resin Thermosetting resin

Isomer
Isotactic Syndiotactic Atactic
Isotactic : When the main chain is placed on one plane," the substituents are
all above or below
Syndiotactic : Substituents alternately present above and below the plane
Atactic : Irregularly arranged substituents

1.3. Molar Mass & Degree of Polymerization
• Many properties of polymers – a strong dependence upon the size of the polymer chains
• Molar mass: the mass of 1 mol of the polymer (g/mol or kg/mol)
• ‘Molecular weight’: still often used instead of molar mass, but is not preferred because it
can be somewhat misleading.  a dimensionless quantity, relative molar mass
• Degree of polymerization (x): the number of repeat units in the polymer chain
• M0: the molar mass of the repeat unit
• For copolymer
- M0 needs to be replaced by 𝑀 (the mean repeat unit molar mass of the copolymer)
- 𝑋 : the mole fraction
- 𝑀 : the molar mass of repeat unit of type ‘j’ in the copolymer
1.3. Molar Mass & Degree of Polymerization
 DP: total number of structural units.
It is closely related to both chain length & molecular weight.
mw of structural unit = 28 g/mol mw of structural unit = 42 g/mol

if DP (n) = 1,000 if DP (n) = 1,000
M.W. = 28 X 1,000 = 86,000 g/mol M.W. = 42 X 1,000 = 42,000 g/mol
mw of structural unit = 86 mw of structural unit = 104 g/mol

if DP (n) = 1,000 if DP (n) = 1,000
M.W. = 86 X 1,000 = 86,000 g/mol M.W. = 104 X 1,000 = 104,000 g/mol
1.3.2. Molar Mass Averages
Molecular masses that are important in determining polymer properties are
the number-average, Mn ( = 1),
the weight-average, Mw ( = 2), and
the z-average, Mz ( = 3), molar mass.
총분자
O 량흡
,
https://www.azom.com/article.a
spx?ArticleID=12255
Polydispersity index (Heterogeneity index)
Polydispersity index (PDI)
The dispersity, formerly the polydispersity index (PDI) or heterogeneity index, is a

measure of the distribution of molecular mass in each polymer sample. PDI of a
polymer is calculated:
중량 분자량,
평균
IUPAC; polydispersity  dispersity, Đ

수평균
A uniform (monodisperse) collection A non-uniform (polydisperse) collection

PDI = 1 PDI = 1.5~2.0
The dispersity indicates the distribution of individual molecular masses in a batch of polymers
Molecular Structure of Polymers
Types of bonds
(1) Primary covalent (2) Hydrogen bond (3) Dipole interaction
(4) Ionic (4) van der Waals
The distinctions are not always clear-cut, that is, hydrogen bonds may be considered as the
extreme of dipole interactions. The secondary bonds are generally weaker bonds and are
responsible for many of the bonds between different polymer chains (intermolecular bonds).
Molecular Structure of Polymers
Bond distances and strengths

Types of Polymers
Bonding and Molecular Structure
The different types of bonds and their effects on the three-dimensional organization of
a polymer.
These are covalent bonds that These are weak bonds between near-
~
C
link monomers and make up neighbor repeat units, covering a

~
1
range of perhaps 10–20 repeat units.
the backbone of the polymer. Hydrogen bonds are common here
and cause an impact on the formation
of coils or zig-zag structures.
These bonds hold the three-

dimensional structure of an These are weak intermolecular bonds (those between
individual polymer in place. two different polymers).
Differences between polymer and small molecules
Difference between polymer and small molecule
Difference in molecular weight Give a difference in physical properties
-Ethane has a molecular weight of about 30, while polyethylene is about 30,000 to
500,000.
<Ethane> <Polyethylene>
Notice!!
• Polymers are actually twisted (Random coiled).

• Therefore, the end-to-end distance is often used.
Difference between polymer and small molecule
1. Difference in viscosity
-A solution in which a low-molecular substance is dissolved has a viscosity similar to that

of a pure solvent as long as the concentration is not large, but the polymer solution
exhibits the viscosity characteristics of a colloidal solution, and the viscosity increases
significantly as the concentration of the solution increases.
Colloid Solution Viscous solution

2. Through the membrane Membrane

Polymer너모써 통과상
-Low molecule can pass through a membrane
such as cellulose acetate, but polymers
cannot. “Polymer is too big”
-Therefore, it is possible to separate low-

molecule and polymers by dialysis.
Molecule
3. Volatility
-Small molecules evaporate well, but polymers do not.

4. Wide range of melting points. Polymer Melting Point

Polyamide 210 ~ 215
-Polymers have a very wide range of melting
points. The reason is that it has an Polycarbonate 220 ~ 360
amorphous region and a crystalline region
Poly urethane 150 ~ 180
together.
PTFE 325 ~ 360
5. Molecular weight distribution
-Small molecules have a certain molecular weight. However, since the polymer has a
constant distribution, the molecular weight is expressed as an average value.
“All five reasons are due to the difference in

molecular weight.”
Summary
• Control of polymer structures

• Many properties of polymers – a strong dependence upon the size of
the polymer chains
2024-Spring
Introduction to Polymers
Chapters 2-3
Department of Energy Science and Engineering
Chiyoung Park
parkcy@dgist.ac.kr
E6-512
Key Concepts
Classification of Polymerization Reactions

The Principle of Equal Reactivity
Linear Step Polymerization =
Stepgrowth Polymenzation
Carothers Theory
Kinetics of Step Polymerization
Process
Non-linear Step Polymerization
Gelation Theory
Dendrimers
Hyperbranched Polymers
Chapter 2
Principles of Polymerization
1.3 Polymerization 2.1. Introduction
l : chaugpottliving
number-average degree of polymerization

Chain Growth Polymerization
.
step growty
Living
Polymerization
Step Growth Polymerization
0 50 100
% conversion
Condensation Polymerization
Addition Polymerization
2.2. Classification of Polymerization Reactions
1) Polymer Composition and Structure

D
Condensation polymers were those polymers that were formed from polyfunctional
monomers by the various condensation reactions of organic chemistry with the elimination of
some small molecule such as water and HCl.
Monomer Monomer
“Functional groups are

@ + @ essential for polymerization”
Functional Groups
Polymerization
+ @
T
Repeating Unit
Degree of polymerization
66
ylon
Condensation polymers
Polyamide
알코 카복실이
OG
Polyester
알코온
Polycarbonate

> 어떻게 Initiation 할지가 중도
③ Addition polymers were classified by Carothers as those formed from monomers without
the loss of a small molecule.
Unlike condensation polymers, the repeating unit of an addition
polymer has the same composition as the monomer.
이중결합
Y Y
e
Monomers containing a carbon–carbon double bond, including monomers such as methyl
methacrylate, vinylidene chloride, and 2-butene as well as vinyl chloride and styrene.
Addition polymers
V
ㄴ
* 2.2. Classification of Polymerization Reactions
Step Growth Polymerization Chain Growth Polymerization

(가괴
6 6 2가지
monomer
monomer
. fast
. ]@
+
I  I 스
.+
Initiation
Consumption of monomers I  I
mm
~ ,
.+ !
]
I
. +n
q
Oligomer formation
Propagation
( )n . +
.
( )n ( )n @
Termination
( )n
2.3. Monomer Functionality & Polymer Skeletal Structure
Chemical rxns proceed as a consequence of

collisions during encounters between mutually
reactive functional groups.
The reactivity of a functional group depends

,
upon its collision frequency and not upon the

collision frequency of the molecule to which it
is attached.
Mathematical analysis of polymerizations is

simplified greatly by assuming that the
intrinsic reactivity of a functional group is
independent of molecular size and unaffected
by the reaction of other functional group(s) in
the molecule of monomer from which it is
derived.
This principle of equal reactivity of functional

groups was proposed by Flory
 step polymerization
 chain polymerization (the reactivity of the
active species at the chain end is
independent of the degree of
polymerization)
Chapter 3
Step Polymerization
3.1. Introduction
Brief Communication: How & Why?
Cold Drawn
Julian Hill, who collaborated

with Wallace Carothers in
early polymer discoveries in
the 1930s.
3.1. Introduction
특허
오쳐 」
https://cen.acs.org/articles/94/i4/DuPont-Shrunk-Central-Research-Unit.html
3.1. Introduction
Step polymerization; in most cases, logical extension of simple organic chemistry linking
reactions to chain formation
Organic chemistry
Polymer chemistry
트
ㅡ
polyesters
polyamides
…
polyurethanes
polycarbonate
epoxy resins
high performance polymers (Kevlar, PEEK)
3.2. Linear Step Polymerization
~
= E
다ㄴ
릭
E
돌
0
RA2 + RB2 ARB

step polymerization step polymerization
3.2.1. Polycondensation
Linear Step Polymerization: Polyesters
RA2 + RB2
step polymerization
⑥ @
θ @
ARB
step polymerization
Recycling: PET
향ㆍ령
국부 경
Poly fethylene terephtalate)

Linear Step Polymerization: Polyamides
RA2 + RB2
step polymerization
ARB
step polymerization
Linear Step Polymerization: Polyethers
• rare example
RA2
• the dehydration of diols
step polymerization • not very controlled
RA2 + RB2 • a much better method for polyethers

step polymerization • polycondensation of dihalides with dialkoxides
• most polyethers are prepared by the ring-opening polymerization of epoxides (Chapter 7)

3.2.1.2. Synthesis of Engineering & High-performance Polymers
by Polycondensation
Aromatic groups: stiffening effect & high stability  improved mechanical properties &
greater resistance to degradation on exposure to heat or radiation
body에그
m
사
기제적강A
벤렌
Bisphen이
1
높
ㅡ
케분다
3.2.1.2. Synthesis of Engineering & High-performance Polymers
by Polycondensation
1
copolymerr
&
3.2.1.3. Synthesis of Conducting Polymers by
Polycondensation
3.2.1.3. Synthesis of Polysiloxanes by Polycondensation
• a completely inorganic backbone of –Si-O- bonds

• high thermal stability
3.2.1.3. Synthesis of Polysiloxanes by Polycondensation
Polysiloxanes for flexible applications
3.2.2 Polyaddition
• Step polymerization in which the monomers react together without the elimination of other
molecules are termed polyadditions.
• In contrast to polycondensation, there are relatively few important polymers prepared by

polyaddition, the most important being polyurethanes and epoxy resins.
3.2.2.1 Synthesis of Linear Polyurethanes and Polyureas by
Polyaddition
RA2 + RB2 polyaddition

of diisocyanates with
diols
• proceeds quite rapidly at room temperature (isocyanate groups are highly reactive)
• catalysts often used to increase the rate of polymerization
• popular diisocyanates • many diols

3.2.2.1 Synthesis of Linear Polyurethanes and Polyureas by
Polyaddition

of diisocyanates with
diamines
• proceeds at very high rates

• intimate mixing of the monomers requires specialist high-speed mixing equipment
3.2.2.2 Other polymers by polyaddition
• Diels-Alder reaction of dienes with dienophiles: [4+2] cycloaddition
EWG
EDG
EDG
EWG retro-reaction
@high temperature
ARB polyaddition
ladder polymer
3.2.2.2 Other polymers by polyaddition
• Bismaleimide resin
3.2.3. Theoretical treatment of linear step polymerization
• The principle of equal reactivity of functional groups is fundamental to simplification of the

theoretical treatment of step polymerization and was shown to be valid for the most
common polymerizations by the experimental studies of Flory.
• On this basis, step polymerization involves random reactions occurring between any two
mutually-reactive molecular species.
• Intrinsically, each of the possible reactions is equally probable and their relative
preponderances depend only upon the relative numbers of each type of molecular species
(i.e. monomer, dimer, trimer, etc.).
• This assumption of equal reactivity is implicit in each of the theoretical treatments of step
polymerization
•
3.2.3.1. Carothers Theory
Carothers Theory
• a simple method to predict the molar mass of polymers by step polymerization
N0: the number of molecules present initially
N: the number of molecules remaining after a time t of polymerization
• Assuming that there are equal numbers of mutually-reactive functional groups
extent of reaction, p
applicable to RA2+RB2, ARB, RA2 polymerizations

in which there is an exact stoichiometric balance in the numbers of
mutually-reactive functional groups
This equation shows that a high monomer conversion is required

to achieve a high degree of polymerization.
Ex) a monomer conversion, p = 98% is required for Xn = 50
p = 99% is required for Xn = 100
Solid-state polymer electrolytes with in-built fast interfacial transport
for secondary lithium batteries
Nature Energy volume 4, pages365–373 (2019)

Carothers Equation: the more general form
The number-average molar mass ( ) is related to by
where is the mean molar mass of a monomer unit and is given by
Stoichiometric imbalance  limit the attainable values of
e.g. RA2+RB2 polymerization  RB2 excess
reactant ratio, r; the ratio of the numbers of the two different types of functional
group (A and B)  NA and NB are respectively, the numbers of A and B functional
groups
NA = rNB
 
N0: the number of molecules present initially

Carothers Equation: the more general form
It’s common practice to define the extent of reaction p in terms of the functional
groups present in minority (i.e. A groups in this case)
NA = rNB
N: the number of molecules remaining

after a time t of polymerization

if r =
3.2.3.2. Kinetics of Step Polymerization
the assumption of equal reactivity of functional groups  simplify the kinetics
the overall rate of reaction as the rate of decrease in the concentration of one or other of the functional
groups, i.e. in general terms for equimolar stoichiometry
general elementary reaction
neglecting elimination products
k’ ; the rate coefficient for the reaction
a true catalyst does not change as the reaction proceeds

 k = k’[catalyst]
equimolar stoichiometry [A] = [B] = c

applicable to no
catalyst reaction
c0 /c = N0 /N
assuming that the reverse reaction

c = c0 at t =0
(i.e. depolymerization) is negligible
Certain step polymerization are self-catalyzed  one of the types of functional groups also act
as a catalyst (e.g. COOH in a polyesterification)
In the absence of an added catalyst the rate of reaction for such polymerizations is given by
assuming that the A groups catalyze the reaction
equimolar stoichiometry [A] = [B] = c
upon integration over the same limits (c = c0 at t =0)
c0 /c = N0 /N
assuming that the reverse reaction

(i.e. depolymerization) is negligible
These results further substantiate the validity of the principle of equal reactivity of functional
groups
3.2.3. Ring Formation
the intramolecular reaction of terminal functional groups on the same molecule

3.2.4. Linear Step Polymerization Processes
PET polymerizations
Interfacial polymerization
H2O
(NaOH)
CCl4
Interfacial polymerization
3.3. Non-linear Step Polymerization
gelation : an abrupt change of the

reacting mixture from a viscous liquid to
a solid gel which shows no tendency to
flow
gel point : the point at which the first

network molecule is formed
3.3.1. Network Polymers
• Network polymers produced by step polymerizations were amongst the first types of
synthetic polymers to be commercialized and often are termed resins.
• The polymerizations must be carried out within a mould to produce the required
artefact.
3.3.1.1. Non-linear Step Polymerization:
Formaldehyde-based resins
Phenolic resin is classified into novolac or resol resin based on the pH and
phenol to formaldehyde ratio used in the reaction.
Novolac type resin : prepared under acidic conditions, and with an excess of
phenol compared to formaldehyde, will be formed.
The shelf life and stability of novolac resins are higher compared with those for
resol resin.
However, an additional catalyst is required to cure novolac resins.
Resol type resins : formed under basic conditions when the molar amount of
formaldehyde exceeds that of phenol.
They are thermosetting resins with methylol and hydroxyl group capable of
forming a cross-linked network without the use of additional curing agents.
This, in itself, represents a significant environmental benefit over novolac resins,
since most curing agents used have toxic effects.
Novolac resin
Resol resin
Urea-Formaldehyde resin
Melamine-Formaldehyde resin
3.3.1.1. Non-linear Step Polymerization: Epoxy resins
Epoxy resins are low molecular prepolymers containing epoxide end-groups.
The most important are the diglycidy ether prepolymers prepared by the reaction of
excess epichlorohydrin with bisphenol-A in the presence of a base
3.3.1.2. Non-linear Step Polymerization: Epoxy resins
These prepolymers are either viscous

liquids or solids depending upon the
value of n.
Usually, they are cured by the use of
multifunctional amines which undergo a
polyaddition reaction with the terminal
epoxide groups in the manner indicated
below (for a diamin, f =4)
Epoxy resins are characterized by low shrinkage on curing and find use as adhesives,
electrical insulators, surface coatings and matrix materials for fibre-reinforced
composites
3.3.1.3. Network Polyurethanes
3.3.1.3. Network Polyurethanes
3.3.2 Gelation Theory
gelation : an abrupt change of the reacting mixture from a viscous liquid to a solid gel which shows no
tendency to flow
gel point : the point at which the first network molecule is formed in a non-linear polymerization
3.3.2 Gelation Theory
Various applications Shale Gas

3.3.2.1 Carothers Theory of Gelation
fav : the number-average functionality

Ni : the initial number of molecules of monomer i which has functionality fi
 if there are N0 molecules present initially, the total number of functional groups present is N0fav
 if at time t there are N molecules present, then the number of functional
groups that have reacted is 2(N0-N) since the number of molecules decreases by
one for each link produced by the reaction together of two functional groups
fav = 2.0
the critical extent of

reaction pc
Non-linear Step Polymerization: Gelation Theory
Dendrimers
Dendrimers
Donald Tomalia
Divergent Synthesis
Convergent Synthesis
T. Kato, Craig Hawker,

Karen Wooley, Jean Frechet
Hyperbranched Polymers
ARBx (x > 2)
J. Poly. Sci. Part A: Poly. Chem. 1998, 36, 1685

ARBx (x > 2)
Nfbr : the number of fully branched monomer units

Nterm: the number of terminal monomer units
Ntotal: the total number of monomer units, including those that are not fully branched
Chem. Soc. Rev., 2015, 44, 4091

Covalent Organic Framework
https://www.nature.com/articles/s43586-022-00181-z
https://www.nature.com/articles/natrevmats201668
Covalent Organic Framework
https://www.nature.com/articles/s43586-022-00181-z
Conclusion
Classification of Polymerization Reactions

The Principle of Equal Reactivity
Linear Step Polymerization
Carothers Theory
Kinetics of Step Polymerization
Process
Non-linear Step Polymerization
Gelation Theory
Dendrimers
Hyperbranched Polymers
• Simple Organic Chemistry  Monomer Functionality  Diverse Polymers

• Linear, Non-linear polymers, Dendrimers, Hyperbranched polymers

고분자개론 1장

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2024-Spring

Heinrich Otto Wieland H. Staudinger

Self-Assembly & Supramolecular Polymers

2000 : Conducting polymers

1991: for discovering that methods

1) Nomenclature Based on Source (IUPAC)

“Depending on whether there is

Random Copolymer Alternating Copolymer

Block Copolymer Graft Copolymer

Dendrimer: Tree-like macromolecules by iterative synthesis

Poly(methylene) Poly(oxyethylene oxyterephthaloyl)

<Random Copolymer> <Graft Copolymer>

• Different monomers randomly bonded

• Different monomers form blocks

<Alternating Copolymer> • Block attached to the side branch

• Different monomers alternately bonded

Poly(methyl methacrylate)-b-poly(n-butyl acrylate)

Poly(methyl methacrylate–co–n-butyl methacrylate)-b-

Thermoplastic Resin Thermosetting resin

Isotactic Syndiotactic Atactic

Atactic : Irregularly arranged substituents

• M0: the molar mass of the repeat unit

mw of structural unit = 28 g/mol mw of structural unit = 42 g/mol

mw of structural unit = 86 mw of structural unit = 104 g/mol

Polydispersity index (PDI)

The dispersity, formerly the polydispersity index (PDI) or heterogeneity index, is a

IUPAC; polydispersity  dispersity, Đ

A uniform (monodisperse) collection A non-uniform (polydisperse) collection

(1) Primary covalent (2) Hydrogen bond (3) Dipole interaction

(4) Ionic (4) van der Waals

Bond distances and strengths

link monomers and make up neighbor repeat units, covering a

These bonds hold the three-

Difference in molecular weight Give a difference in physical properties

• Polymers are actually twisted (Random coiled).

-A solution in which a low-molecular substance is dissolved has a viscosity similar to that

Colloid Solution Viscous solution

2. Through the membrane Membrane

-Therefore, it is possible to separate low-

-Small molecules evaporate well, but polymers do not.

4. Wide range of melting points. Polymer Melting Point

5. Molecular weight distribution

“All five reasons are due to the difference in

• Control of polymer structures

Classification of Polymerization Reactions

number-average degree of polymerization

Step Growth Polymerization

1) Polymer Composition and Structure

“Functional groups are

1) Polymer Composition and Structure

1) Polymer Composition and Structure

1) Polymer Composition and Structure

Step Growth Polymerization Chain Growth Polymerization

Chemical rxns proceed as a consequence of

The reactivity of a functional group depends

upon its collision frequency and not upon the

Mathematical analysis of polymerizations is

This principle of equal reactivity of functional

Julian Hill, who collaborated

RA2 + RB2 ARB

Poly fethylene terephtalate)

RA2 + RB2 • a much better method for polyethers

• most polyethers are prepared by the ring-opening polymerization of epoxides (Chapter 7)

• a completely inorganic backbone of –Si-O- bonds