Course title

Subject code: PCPO322512

Instructor: Dr. Thanh-Truc Pham

Email: trucpt@hcmute.edu.vn
 Chapter I
Introduction of polymers

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CONTENTS

I. History of polymer industry development

II. Basic concepts
III. Nomenclature
IV. Classification of polymers

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I. History of polymer industry development

1910 1930-1940
1810

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CONTENTS

I. History of polymer industry development

II. Basic concepts
III. Nomenclature
IV. Classification of polymers

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II. Basic concepts

Polymer

Monomer Repeating Unit Polymer

Styrene Polystyrene Polystyrene
Oligomer

Monomer Polymer
Monomer Caprolactone Polycaprolactone

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II. Basic concepts
Bonding in polymers

Ionic
ATOMIC BONDING

Primary Covalent
Coordinated covalent
Metallic

Dispersion
Secondary Polar
Induced polar
Hydrogen
Kevlar

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II. Basic concepts

How to define the size of a polymer molecule?

• Degree of polymerization (DP - độ trùng hợp)
• Molecular weight or molar mass (khối lượng phân tử)
• Fully extended molecular length (chiều dài)

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II. Basic concepts
How to define the size of a polymer molecule?
• Degree of polymerization

Main chain
Polymerization
Degree of polymerization
𝑀𝑝𝑜𝑙𝑦𝑚𝑒𝑟
𝐷𝑃𝑛 =
𝑀𝑟𝑒𝑝𝑒𝑎𝑡 𝑢𝑛𝑖𝑡

Substituent group

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II. Basic concepts
How to define the size of a polymer molecule?
Molecular weights 1,2
The numbers of molecules Ni having molecular weight Mi
σ∞
𝑖=0 𝑁𝑖 𝑀𝑖
Number-average MW 𝑀𝑁 = σ∞
𝑖=0 𝑁𝑖 Wi
= NiMi
σ∞ 2
𝑖=0 𝑁𝑖 𝑀𝑖
Weight-average MW 𝑀𝑊 = σ∞
𝑖=0 𝑁𝑖 𝑀𝑖

σ∞ 3
𝑖=0 𝑁𝑖 𝑀𝑖
Z-average MW 𝑀𝑧 = σ∞ 2
𝑖=0 𝑁𝑖 𝑀𝑖

1+𝑎 1/𝑎
σ∞
𝑖=0 𝑁𝑖 𝑀𝑖
Viscosity-average MW 𝑀𝑉 = Mn Mv Mw Mz
σ∞
𝑖=0 𝑁𝑖 𝑀𝑖

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II. Basic concepts
How to define the size of a polymer molecule?
• Molecular weights 1,2

HOW BIG
IS BIG?

M = 103 ~ 107

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II. Basic concepts
How to define the size of a polymer molecule?
• Molecular weights
𝑀𝑤
• Polydispersity index (PDI) – chỉ số đa phân tán: 𝑃𝐷𝐼 =
𝑀𝑛

𝑃𝐷𝐼 = 1 𝑃𝐷𝐼 > 1

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II. Basic concepts
How to define the size of a polymer molecule?
• Molecular weights 1,3 – Methods for determining MW
Primary methods Secondary methods
(Direct method) (Indirect methods)
Osmotic pressure (𝑀𝑁 ) Fractional precipitation
Intrinsic viscosity (𝑀𝑁 ) Gel permeation chromatography (GPC)
Ultracentrifuge sedimentation (𝑀𝑊 , 𝑀𝑍 ) High-performance liquid chromatography
Diffusion (𝑀𝑊 ) (HPLC)
Light scattering (𝑀𝑊 ) Electrophoresis

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II. Basic concepts
How to define the size of a polymer molecule?
Example
Calculate the number-average and weight-average molar mass and polydispersity
index of the following ternary mixture of monodisperse polymer samples, each
characterized by molar mass, Mi, and number of moles, Ni, as reported in the
following table 4:

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II. Basic concepts
How to define the size of a polymer molecule?
Example
Number-average molar mass:
σ∞
𝑖=0 𝑁𝑖 𝑀𝑖 0.053 × 10000 + 0.035 × 50000 + 0.012 × 100000
𝑀𝑛 = = = 34800
σ∞ 𝑁
𝑖=0 𝑖 0.053 + 0.035 + 0.012

Weight-average molar mass:

σ∞
𝑖=0 𝑁𝑖 𝑀𝑖
2
0.053 × 100002 + 0.035 × 500002 + 0.012 × 1000002
𝑀𝑊 = ∞ = = 61149
σ𝑖=0 𝑁𝑖 𝑀𝑖 0.053 × 10000 + 0.035 × 50000 + 0.012 × 100000

Polydispersity index:
𝑀𝑤 61149
𝑃𝐷𝐼 = = = 1.76
𝑀𝑛 34800
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II. Basic concepts
How to define the size of a polymer molecule?
• Molecular length 1

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II. Basic concepts
How to define the size of a polymer molecule?
• Molecular length 6
Example: Calculate the molecular length of a following molecule with n = 104.

𝐿𝐶−𝐶 = 2 × 0.1542 × (1 − 𝑐𝑜𝑠109.5°) 1/2

= 𝟎. 𝟐𝟓𝟐 𝒏𝒎
LC-C
𝐿 = 𝑛 × 𝐿𝐶−𝐶 = (104 )1/2 × 0.252𝑛𝑚
L=? = 𝟐𝟓. 𝟐 𝒏𝒎

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CONTENTS

I. History of polymer industry development

II. Basic concepts
III. Nomenclature
IV. Classification of polymers

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III.Nomenclature

Basic concepts according to IUPAC:

poly{[(locants-……)]}
Examples: poly(4-chlorostyrene), poly(1,4-divinylbenzene)
or poly ……
Examples: polystyrene, polyisoprene
or end group-poly…
Examples: -chloro--hydroxy-polystyrene

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III.Nomenclature
Traditional Names
polyethylene
polypropylene
polystyrene
…

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III.Nomenclature
Source-based Nomenclature when monomer can be identified.
• Homopolymer: “poly” + class name:monomer name

“poly” + monomer name: poly(vinyloxirane)  Unclear

“poly” + class name:monomer name: polyalkylene:vinyloxirane (left)
polyether:vinyloxirane (right)

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III.Nomenclature
Source-based Nomenclature
• Copolymer:

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III.Nomenclature
Source-based
Nomenclature
• Non-linear polymers

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III.Nomenclature
Structural-based Nomenclature
• Regular single-strand organic polymers preferred constitutional repeating unit (CRU)
i. CRU must show the structural repetition;
ii. CRU is the smallest;
iii. Identify subunits – The largest divalent groups;
iv. Using the shortest path of the most senior subunit to the next senior;
v. Lowest locants for substituents.

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III.Nomenclature

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III.Nomenclature

The order of subunit seniority.

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 III.Nomenclature
Structural-based Nomenclature Polymer name: poly[oxy(1-bromoethane-1,2-diyl)]

• Regular single-strand organic polymers CRU name: oxy(1-bromoethane-1,2-diyl)

Subunit Seniority: oxy > 1-bromoethane-1,2-diyl

oxy 1-bromoethane-1,2-diyl

Possible CRU

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III.Nomenclature
Structural-based Nomenclature
• Regular double-strand organic polymers
i. Consist of uninterrupted chains of rings.
ii. CRU: max number of heteroatoms & min number of free valances.
Polymer name: poly(butane-1,4:3,2-tetrayl)

CRU name: butane-1,4:3,2-tetrayl (clockwise order)

Possible CRU
Subunit: acyclic of 4 carbon
Lower left atom atoms with 4 free valences
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III.Nomenclature
Inorganic & Inorganic-Organic Polymers
• Regular single-strand inorganic polymers are named like organic polymers or with
inorganic nomenclature (different seniority).
• Inorganic-organic polymers are named like organic polymers.

Polymer name: poly[(dimethylsilanediyl)ferrocene-1,1’-diyl]

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CONTENTS

I. History of polymer industry development

II. Basic concepts
III. Nomenclature
IV. Classification of polymers

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IV. Classification of Polymers

By their thermal response

• Thermoplastics (nhựa nhiệt dẻo) – Amorphous and Crystallite
• Thermosets (nhựa nhiệt rắn)
• Elastomers (đàn hồi)

By origins
• Natural polymers (polymer tự nhiên)
• Semisynthetic polymers (polymer nhân tạo)
• Synthetic polymers (polymer tổng hợp)

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IV. Classification of Polymers
By mode of formation
• Additional polymers (polymer trùng hợp)
• Condensation polymers (polymer trùng ngưng)

By structures

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IV. Classification of Polymers

By tacticity

• Isotactic • Syndiotactic • Atactic

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IV. Classification of Polymers

By the arrangement of monomers

• Homopolymer
• Copolymer

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Summary

1. Which parameters define the size of a polymer?

2. How to calculate the MW of a polymer?
3. Determine the repeat unit of a polymer.
4. Classification of polymers.

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References
1. Davis, Fred J., ed. Polymer chemistry: a practical approach. Oxford University Press on Demand, 2004.
2. Sperling, Leslie H. Introduction to physical polymer science. John Wiley & Sons, 2005.
3. Odian, George. Principles of polymerization. John Wiley & Sons, 2004.
4. Cowie, John Mackenzie Grant, and Valeria Arrighi. Polymers: chemistry and physics of modern
materials. CRC press, 2007.
5. Nicholson, John. The chemistry of polymers. Royal Society of Chemistry, 2017.
6. Hiemenz, Paul C. Polymer Chemistry-The Basic Concepts, Mar-cel Dekker. Inc. New York and Basel
(1984): 211-215.
7. Jasso-Gastinel, Carlos Federico, and José M. Kenny, eds. Modification of polymer properties. William
Andrew, 2016.

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