Introduction to Polymer

ch1
 What is Polymer?
 Polymer: Poly (many) + meros (part, or unit)
polymers are large molecules made up of simple repeating
units called Monomer (M)

(Macromolecule)

—M—M—M—M—M—M—
or
—(M)n —
Examples of monomers and polymers

Monomer (M) Polymer -(M)n-

CH2 CH2
CH2CH2

CH2 CHCl CH2CH2

Polymerization Cl
O
H2C CH2 CH2CH2O

HOCH2CH2OH CH2CH2O

HO CO2H O C
Monomer Resources

Coal
Petroleum
Natural gas
Biomass (renewable)
 Monomers from renewable resources
(ref. Biocatalysts in Polymer Chemistry, 2011 Willy-VCH)

 Terpenes, Sugars
 Glycerol and the derivatives, Furans
 Vegetable oils, Tannins and lignin fragment
 Miscellaneous
CH2-CH
 “Polymerization”

Thermoplastic
Hard solid
Colorless liquid
Mw: 104
bp: 145°C (PS)
 산과 일코올이 만남 그물을 만들며 결합
M1 ~ '
M2 Polymerization => 에스터 생성
M
1
2개

PET common thermoplastic polyester

in fiber, film, bottle, etc
 Why Polymer?
Molecular size effect on physical state and property of
organic molecule (ex. alkane series)
DP MW Physical State Mp (oC) BP (oC/mmHg)
냄대서
1 30 gas -172 -88.5/760
김수
5 142 liquid -30 174/760
10 282 crystalline solid 37 205/15
30 842 crystalline solid 99 259/10-5
60 1682 waxy solid 100 dec
100 2802 fragile solid 106 dec
1000 28002 Tough plastic 110 dec

* DP of PE: 1,000 ~
10,000, mp 110-130 oC
Molecular Weight vs Property

Property

MW

MW-property relationship
 Polymer Classification

 By Origin (or Source)

 By Composition and Monomer Sequence
 By Chain Structure (or Topology)
 By Type of Polymerization Reaction
 By Polymer Growth Mechanism
 By Thermal Response (thermoplastic / thermoset)
 By Morphology (amorphous / crystalline)
 Polymer Classification

□ Based on Source

Natural: cellulose, starch, silk, chitin, natural rubber,

protein, DNA (Biomacromolecules)

Synthetic: PE, PP, PVC, polyesters, polyamides, PU….

Semi-Synthetic or Modified Natural: cellulose acetate, rayon ..

eponidized rubber
Natural Polymers
: Cellulose, Starch, Natural Rubber, Lignin, Protein, Nucleic acid
□ Based on Composition:
Homopolymer and Copolymers
Homopolymer : -A-A-A-A-A-A-A-A-

Random copolymer : -A-B-B-A-B-A-A-B-

Alternating copolymer : -A-B-A-B-A-B-A-B-

Block copolymer : -A-A-A-A-B-B-B-B-

Graft copolymer : -A-A-A-A-A-A-A-A-

B-B-B-B-B-
□ Based on Chain Structure
: Linear, Branched and Crosslinked (network) Polymer
Linear polymers may be represented by a chain with two ends.
Linear chain does not imply “straight” molecules.
They can curl, twist or fold

Branched polymers have side chains, or branches, of

significant length which are bonded to the main chain at
branch points, and are characterized in terms of the number
and size of the branches.
Polymers with well-controlled modes of branching:
Comb-like polymers, star polymers, dendrimers, etc.

Network polymers have three-dimensional structures in which

each chain is connected to all others, and are characterized by
their crosslinking density or degree of crosslinking (number of
junction points per unit volume).
Various Chain Architecture
□

Addition polymer: repeating units contains same atoms as the

monomers
(e.g. vinyl polymer, polyolefin...)

작용기수
Condensation polymer: repeating units and monomers are
~

not equal, to be split out small molecule

H , 0 M 디동 kct 생업
(e.g. polyester, polyamide, ….)
.

Bm
.

 Ring Opening Polymer

 Remember that Polymer might well be synthesized by either addition,

condensation or ring-opening polymerization
여러 방식으로 가능
Example

Polyester
~ "
Ring
카복기산이 떠올 나야함

condensation

Polyamide

In some cases, one polymer can be synthesized by both types of

polymerization reaction, so this classification is not always clear !!
Polyurethane

Polyethylene
□ Based on the polymerization mechanism

Step-growth polymer
most condensation polymers,
polymer build up stepwise throughout monomer matrix
applies to monomers with functional groups such as alcohol, amine,
carboxylic acid, etc 반응을 통해서 ⇒ 천천히 스텝
반복 polymer
Chain-growth polymer
>

most addition polymers,

polymer build up by successive addition of monomer to the growing
chain.
applies to monomers having double bonds or ring structure
빠르게 연결 연결 연결
<Step-growth Mechanism>

Extent of reaction
말단의 농도는 d
Ex. Step-growth polymerization via condensation
(polyesterification, polyamidation, etc)

A-B type

HO COOH

A-A + B-B type

HOOC COOH + HOCH2CH2OH

“ exact stoichiometric balance and monomer purity”

is necessary for high mw polymer synthesis !
 복세
발응 X > radical필요 =>
gonevaton =⇒
polymr
<Chain-growth Mechanism>
중간에 서 사용 가능 But Step growth - m 는 안됨

Extent of reaction
 Ex. Chain-growth polymerization
(vinyl addition polymerization, ring-opening polymerization)

II

PS

PEG
Brng opeevag
> charn
-

grath
참고
Most step-growth polymer is condensation processes, and
Most chain-growth polymer is addition processes. But there are exceptions !

Step-reaction addition (a) and

Chain-reaction condensation (b)

(a)

(b)

분언은 나동 Bat chen

□ Based on thermal processing behavior

Thermoplastics
PS, PVC, Polyolefins (PE, PP ...), PET, Nylon…

Thermosets
Epoxy, Phenol-Formaldehyde,
Unsaturated Polyester …
□ Based on thermal processing behavior

Thermoplastics
결정유지
도달하기까지
PS, PVC, Polyolefins (PE, PP ...), PET, Nylon…
Tm 까지

θ
Thermosets
Epoxy, Phenol-Formaldehyde,
@ O
Unsaturated Polyester …
비결정성

semicrystalline
 Polymer Nomenclature (Naming)

Poly ( ? )

1. Source-based name: common name of monomer preceded by

prefix ‘Poly’
2. Structure-based name: IUPAC name

 Linkage-based name: ‘family’ name

 Trade names, Brand names, and Abbreviations
Naming Alkanes Me than e

• International Union of Pure and Applied

Chemistry (IUPAC) system of nomenclature
치환기가 붙은 위치 치환가 성씨 접미사

• Steps in naming in complex branched-chain

alkanes
• Find parent hydrocarbon chain
• Identify the longest continuous chain of carbon
atoms, use the name of that chain as the parent
name

© 2016 Cengage Learning. All Rights Reserved.

Naming Alkanes
Parent
sh
챽긽 material Union Pure Applied Chemistry
IUPAC

• If two different chains of equal length are present,

choose the one with the larger number of branch
points as the parent
치환기가 많은 경우로 묘 - 치환기 복잡

© 2016 Cengage Learning. All Rights Reserved.

Naming Alkanes
• Number the atoms in the longest chain
• Beginning at the end nearer the first branch point,
number each carbon atom in the parent chain
치환기 숫자가
작도록 넘버링

• If there is branching at an equal distance away from

both ends of the parent chain, begin numbering at
the end nearer to the second branch point
첫번째가 같다면
두번째가 잘은 걸로

© 2016 Cengage Learning. All Rights Reserved.

Naming Alkanes
• Identify and number substituents
• Assign a number, or locant, to each substituent to
locate its point of attachment to the parent chain

• If there are two substituents on the same carbon,

give both the same number

© 2016 Cengage Learning. All Rights Reserved.

Naming Alkanes
• Write the name as a single word

알파벳 순

r 우선순위 결정x

© 2016 Cengage Learning. All Rights Reserved.

Naming Alkanes
• Name a branched substituent as though it were
itself a compound

© 2016 Cengage Learning. All Rights Reserved.

cit
나
)

vinyliodine
PEO
• Many vinyl copolymers in industry:
: EPR, EPDM, SAN, EVA, ABS, SIS, etc.

- IUPAC recommend source-based name of copolymers

Poly[styrene-co-(methyl methacrylate)] systematic
Copoly(styrene/methyl methacrylate) concise

- In place of co, ran, alt, block, or graft are used to specify the
monomer sequence along the chain.

- With graft copolymers, the order of monomer name is important.

ex1. Polystyrene-graft-poly(methyl methacryate)

ex2. Polybutadiene-block-(polystyrene-graft-polyacrylonitrile)
 Industrial Polymers 순으로 1
빠르게
 The world consumption of synthetic polymers ㅂ
: ~350
I이Np million metric tons per year.
21기
1) Plastics : 56%
2) Fibers : 18%
3) Synthetic rubber : 11%
4) Coating / Adhesives : 15%

 Five major classifications of the polymer Industry (or application)

: plastics, fibers, elastomers, adhesives, and coatings

 A given polymer may fit into more than one category.

ex. Styrene-butadiene copolymer serve as both a rubber and paint,

Poly(ethylene terephthalate), PET, as both plastic and fiber
 Industrial Polymers
Plastics
1) Commodity plastics
LDPE, HDPE, PP, PVC, PS cf) Table 1.4

2) Engineering plastics
Acetal, Polyamide, Polyamideimide, Polyarylate,
Polybenzimidazole, etc. cf) Table 1.5

3) Thermosetting plastics
Phenol-formaldehyde, Urea-formaldehyde,
Unsaturated polyester, Epoxy,
Melamine-formaldehyde cf) Table 1.6

4) Functional plastics
Optics, Biomaterial, etc.
TABLE 1.4 Commodity Plastic
Type Abbreviation Major Uses

Low-density Packaging film, wire and cable insulation,

LDPE
polyethylene toys, flexible bottles housewares, coatings

High-density HDPE Bottles, drums, pipe, conduit, sheet, film,

Polyethylene wire and cable insulation

Polypropylene PP Automobile and appliance parts, furniture,

cordage, webbing, carpeting, film packaging
Construction, rigid pipe, flooring, wire
Poly(vinyl chloride) PVC
and cable insulation, film and sheet

Polystyrene PS Packaging (foam and film), foam

insulation appliances, housewares, toys
TABLE 1.5 Principal Engineering Plastics

Type Abbreviation Chapter Where Discussed

Acetala POM 11
Polyamideb 13
Polyamideimide PAI 13
Polyarylate 12
Polybenzimidazole PBI 17
Poltcarbonate PC 12
Polyeseterc 12
Polyetheretherketone PEEK 11
Polyetherimide PEI 11
Polyimide PI 13
Poly(phenylene oxide) PPO 11
Poly(phenylene sulfide) PPS 11
Polysulfoned 11
 TABLE 1.6 Principal Thermosetting Plastics
Chapter Where
Type Abbreviation Typical Uses Discussed
Phenol-formaldehyde PF Electrical and electronic equipment, 1
automobile parts, utensil handles, 4
plywood adhesives, particle board
binder
Urea-formaldehyde UF Similar to PF polymer; also 1
treatment of textiles, coatings 4
Unsaturated polyester UP Construction, automobile parts, boat
hulls, marine accessories, 12
corrosion-resistant ducting, pipe,
tanks, etc., business equipment
Epoxy - Protective coatings, adhesives,
electrical and electronics 11
applications, industrial flooring
highway paving materials,
composites
Melamine-formaldehyde MF Similar to UF polymers; decorative
14
panels, counter and table tops,
dinnerware
Plastics

High Performance
Plastics

Engineering
Plastics

Commodity
Plastics
 Industrial Polymers
Fibers
1) Cellulosic :

Acetate rayon, Viscose rayon

2) Noncellulosic :

Polyester: PET
Nylon: Nylon6,6, Nylon6, etc
Olefin: PP, Copolymers of PVC (with AN, VAc, VDC)
Acrylic: Copolymer contain at least 80% acrylonitrile(AN)
TABLE 1.7 Principal Synthetic Fibers

Type Description

Cellulosic
Acetate rayon Cellulose acetate
Viscose rayon Regenerated cellulose

Noncellulosic
Polyester Principally poly(ethylene terephthalate)
Nylon Includes nylon 66, nylon 6, and a variety of other aliphatic and
aromatic polyamides
Olefin Includes polypropylene and copolymers of vinyl chloride, with
lesser amounts of acrylonitrile, vinyl acetate, or vinylidene
chloride (copolymers consisting of more than 85% vinyl
chloride are called vinyon fibers)
Acrylic Contain at least 80% acrylonitrile; included are modacrylic fibers
comprising acrylonitrile and about 20% vinyl chloride or
vinylidene chloride
 Industrial Polymers
Rubber (Elastomers)
1) Natural rubber : cis-1,4-Polyisoprene

2) Synthetic rubber :

Styrene-butadiene, Polybutadiene,
Ethylene-propylene(EPDM), Polychloroprene, Polyisoprene,
Nitrile, Butyl, Silicone, Urethane

3) Thermoplastic elastomer :
Styrene-butadiene block copolymer
(SB or SBS)
TABLE 1.8 Principal Types of Synthetic Rubber
Type Description

Styrene-butadiene Copolymer of the two monomers in various proportions depending on

properties desired; called SBR for styrene-butadiene rubber
Polybutadiene Consists almost entirely of the cis-1,4 polymer

Ethylene- Often abbreviated EPDM for ethylene-propylene-diene monomer;

propylene made up principally of ethylene and propylene units with small
amounts of a diene to provide unsaturation

Polychloroprene Principally the trans-1,4polymer, but also some cis-1,4 and 1,2
polymer; also known as neoprene rubber

Polyisoprene Mainly the cis-1,4 polymer; sometimes called “synthetic natural rubber”
Nitrile Copolymer of acrylonitrile and butadiene, mainly the latter
Butyl Copolymer of isobutylene and isoprene, with only small amounts of
the latter
Silicone Contains inorganic backbone of alternating oxygen and methylated
silicone atoms; also called polysiloxane (Chap. 15)
Urethane Elastomers prepared by linking polyethers through urethane groups
(Chap. 13)
 Industrial Polymers
Coating and Adhesives

1) Coating :

Lacquer, Vanishes, Paint (Oil or Latex), Latex

2) Adhesive :

Solvent based, Hot melt, Pressure sensitive, etc.

Acrylate, Epoxy, Urethane, Cyanoacrylate
 Where does the polymer come from?

Low MW
Carbon
Source

?
PET
Review Exercise (in class)

1. Consider the room you are in while doing homework (dorm room, library,
cafeteria, pub, and so on)
(a) Identify five items in it that are made of polymers.
(b) What would you make those items of if there were no polymers?
(c) Why do you suppose polymers were chosen over competing materials (if any)
for each particular application?

2. In most instances, end group contribute very little to the physical properties
of polymers. With which types of polymers would you expect end groups to
contribute significantly? 예외 ) end gap의 분자량이 크면 그 못들음
…

3. What is the average degree of polymerization of LDPE having an average

molecular weight of 28,000?

4. The first commercially available polyamide fiber was poly(iminohexane-1,6-

diyliminoadipoyl). Write the structure, and suggest two alternate names.
https://www.sigmaaldrich.com/KR/ko/products/materials-science/
biomedical-materials/polyethylene-glycol

PEG I PEO

시
70
시천수성
HcHbL
,

일 =
김수성
(continued)

5. What is the structure of the repeat unit in (a) polypropylene,

(b) poly(vinyl chloride), (c) hevea rubber? [cf. Gutta percha, naturally
occurring trans isomer of polyisoprene]

6. In general, how do the properties of network polymers differ from

those of linear or branched polymers?

7. Look at the bottom of several containers. Identify what the bottles

are made of from the following recycling codes found on their
bottoms: (a) 4 with the letters LDPE, (b) 6 with the letter PS, and
(c) 5 with the letters PP.

8. How can we become more environmentally responsible?

 Review Exercises (text ch1)

Problem #: 6, 7, 9, 10, 13, 15, 18

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