Polymer Chemistry

Li Guang Hua (李光华)

Lab：材料楼 —409#，321#
E-mail : lighua@gmail.com
Cell phone: 15978133590

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 TEXTBOOK & RESULTS

Textbook:
《 Polymer Chemistry》—自编
1. M.P. Stevens, “Polymer Chemistry: an introduction”, Third edition, 1999.
2. G. Odian, “Principles of Polymerization”, Fourth edition, 2003.
3. F.W. Billmeyer, “Textbook of Polymer Science”, Third edition, 1984.
4. A. Ravve, “Principles of Polymer Chemistry”, Second edition, 2000.

Results:
1. 考勤：10% (缺勤一次: －2分；迟到3次=缺勤一次；5次以上：F)
2. 平时成绩：20% （作业，上课表现）
3. 期末考试：70%

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 DATABASES & JOURNALS

Databases:
1. 中文科技期刊数据库，外文科技期刊数据库
2. ACS: 收录 41种期刊 (24种期刊—创刊 ~ 至今)

3. ScienceDirect: 收录 1772种期刊 (1995年 ~至今)

— 世界最大的电子数据库

4. Wiley InterScience: 收录 479种期刊 (1997年 ~ 至今)

5. SciFinder: 提供科学全领域的文献和专利的题目, 出处和概要.

Journals:
Hundreds of kinds

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 CONTENTS

Principles of Polymer Chemistry:

1. Basic Principles
2. Step Polymerization
3. Free Radical Polymerization
4. Ionic Polymerization
5. Coordination Polymerization
6. Chemical Reactions of Polymers

Polymer Materials:
7. Hydrocarbon Plastics and Elastomers
8. Other Carbon-chain Polymers
9. Heterochain Thermoplastic Polymers
10. Thermosetting Resins

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 CHAPTER 1

Basic Principles:
1. Introduction
2. Definitions
3. Polymerization Processes
4. Nomenclature of Polymers
5. Molecular Weight
6. Microstructure of Polymers
7. Physical State
7.1 Crystalline and Amorphous behavior
7.2 Thermal Transitions
8. Industrial Polymers
9. Historical Development

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 1. INTRODUCTION (I)

Three large props of modern civilization

Energy Materials Information

Metals Polymers Ceramics

Plastics Fibers Elastomers Coatings Adhesives

(Rubbers)

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 1. INTRODUCTION (II)

We live in a polymer age

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 1. INTRODUCTION (III)

Polymer chemistry

Research the synthesis and reactions of polymers

Mechanism; kinetics;
influence factor; preparation techniques
Polymer
Polymer physics
science
Research the relations between polymer structure
and properties

Polymer engineering

Research the principles and technology of

polymer molding and engineering of polymerization

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 1. INTRODUCTION (IV)

(polymer synthesis)
Synthesis Structure

(polymer physics)

Application Property
(polymer processing)

Direction of the green arrows :

polymer design

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 1. WHAT IS POLYMER?

Polymer : “poly” + “mer”

many part/unit

A large molecule comprised of repeating units (RU) joined by

covalent bonds.
Repeating unit
Covalent bond

Hermann Staudinger (GER) (1953 Nobel prize)

In 1926, suggest: Hoch-molekül (巨大分子)

unify
High molecule (UK) Polymer

高分子 (JP) 高分子 (CHN)

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 1. WHAT IS POLYMER?

High polymer, Polymer = macromolecule

高聚物 聚合物，高分子 大分子

Classification of molecules according to molecular weight:

Small molecule or low molecule < 1,000

Oligomer (低聚物 or 齐聚物) 1,000 ~ 10,000

RU more than one or lack one influence properties.

Polymer (聚合物) > 10,000

RU more than one or lack one hardly influence properties.

Ultrahigh molecular weight polymer (UHMWP) > 1,000,000

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 2. DEFINITIONS (I)
Monomer, polymerization, polymer
Polymers are synthesized from simple molecules called
monomers by a process called polymerization (PZN).

PZN
CH2 CH2 CH2CH2 n

Monomer Polymer Repeating unit (RU)

or Structural unit (SU)
PZN
CH2 CH CH2CH
Cl Cl n

Monomer Polymer

Vinyl monomer ( CH2 CH ) Vinyl polymer

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 2. DEFINITIONS (II)
PZN
n HOOC COOH + n HOCH2CH2OH

Monomer Monomer
O O
HO C COCH2CH2O H + (2n-1) H2O
n
SU SU

RU

O
PZN
n HO COOH H O C OH + (n-1) H2O
n

Monomer RU = SU
Polymer
Nonvinyl monomer
(Difunctional compounds) Nonvinyl polymer

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 2. DEFINITIONS (III)
Degree of PZN (DP, 聚合度)
refers to the total number of structural units (SU)

F For vinyl polymers

CH2CH2 n CH2CH DP = n (RU=SU)

Cl n MW = n ×M0 = DP ×M0

F For nonvinyl polymers

O O

HO C COCH2CH2O H DP = 2n (RU = 2SU)

n
MW = n ×M0 = (DP/2) ×M0
O
DP = n (RU=SU)
H O C OH
n
MW = n ×M0 = DP ×M0
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 2. DEFINITIONS (IV)
End group
The atom or group at the end of a polymer chain.

C H 3C H 2 C H 2C H 2 CH CH2
n

Telechelic polymer (遥爪聚合物 ): containing reactive end groups ( )

Main chain (or backbone)

H H H H H H
C C C C C C main chain (主链 )
H Cl H Cl H Cl side group (侧基 )
poly(vinyl chloride)

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 2. CLASSIFICATION OF POLYMERS (I)

F Based on element forms of main chain

Ø Carbon chain polymer (碳链聚合物 ) : single atom C
CH2CH2 PE
n

Ø Heterochain polymer : containing O, N, P, etc. besides C

O O O O
C COCH2CH2O NH(CH2)6NHC(CH2)4C n
n
PET Nylon 6,6

Ø Elementary organic polymer (元素有机聚合物 ):

containing Si, B, Al, O, N, P etc. without C
R
Si O Silicone resin
R n

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 2. CLASSIFICATION OF POLYMERS (II)

F Based on kinds of monomer

Ø Homopolymer : prepared from a single monomer
A A A A A A A A

Ø Copolymer : prepared from two or more monomers

A B B A B A A B Random copolymer
(无规共聚物 )

A B A B A B A B Alternating copolymer
(交替共聚物 )

A A A A B B B B Block copolymer
(嵌段共聚物 )
A A A A A A A A
Graft copolymer
B B B B B (接枝共聚物 )

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 2. CLASSIFICATION OF POLYMERS (III)

F Based on molecular architectures

linear polymer branched polymer network polymer

star polymer comb polymer ladder polymer

dendrimer (树枝状聚合物)
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 2. CLASSIFICATION OF POLYMERS (IV)

Linear polymer crosslinking

network polymer
Branched polymer

Soluble in solvents Insoluble (only swelling)

Melt Not melt
Process repeatedly Not process repeatedly

Thermoplastics Thermosetting Resin

(热塑性塑料) (热固性树脂)

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 2. CLASSIFICATION OF POLYMERS (V)

F Based on polymer sources

Ø Natural polymer : cotton, wool, silk, protein, etc.
Ø Synthetic polymer : PE, PP, PVC, PET, nylon 6,6, etc.

F Based on physical properties or end use

Ø Plastics : LDPE, HDPE, PP, PVC, PS, etc.
Ø Fibers : PET, nylon 6,6, PAN, PP, etc.
Ø Elastomers (rubbers) : SBR, EPR, PU, etc.
Ø Coatings : styrene-butadiene copolymer, etc.
Ø Adhesives : epoxy resin, etc.

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 3. PZN PROCESSES (I)
Suggestion of Carothers (1929)

Addition polymer Monomer = RU in composition

(加聚物)
Polymer Addition PZN
n CH2 CH2 CH2CH2
n

Condensation polymer Monomer ≠ RU in composition

(缩聚物)

n HOOC COOH + n HOCH2CH2OH

Condensation PZN

O O
HO C COCH2CH2O H + (2n-1) H2O
n

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 3. PZN PROCESSES (II)
O O
n O C Addition PZN?
O R C
n
R
Addition polymer ?

O
n HO R COOH Condensation PZN H O R C nOH + (n-1)H2O

Condensation polymer

Suggestion of Flory (1951)

According to the mechanism of PZN
Step-reaction or step-growth PZN (step PZN) (逐步聚合)
PZN
Chain-reaction or chain-growth PZN (chain PZN)
(链式聚合 or 连锁聚合)

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 3. PZN PROCESSES (III)
Step PZN

n HOOC COOH + n HOCH2CH2OH

O O

HO C COCH2CH2O H + (2n-1) H2O

n

Ø No reactive center
Ø Growth occurs by the stepwise reaction between the functional
groups of reactants (monomer, oligomer, polymer)

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 3. PZN PROCESSES (IV)

monomer + monomer k dimer

k trimer
dimer + monomer
k tetramer
dimer + dimer
trimer + monomer k tetramer
trimer + dimer k pentamer
tetramer + monomer k pentamer

k (m+n)-mer
In general m-mer + n-mer

Ø The reaction rate and activation energy of every step are

approximately equal.

Ø Reaction system: a series of different molecular weight species

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 3. PZN PROCESSES (V)

Ø Monomer consumed rapidly while MW increases slowly

Most condensation PZN belong to step PZN

Molecular weight

Step PZN

0 20 40 60 80 100
Conversion %

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 3. PZN PROCESSES (VI)
Chain PZN

H H H
CH2=CHY CH2=CHY
I R* R CH2 C* R CH2 C CH2 C*
Y Y Y

H H H
(m-1) CH2=CHY termination CH2 C
R CH2 C CH2 C*
Y m Y Y n

Ø Have reactive center

R* : cation R+, anion R–, free radical R·

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 3. PZN PROCESSES (VII)

Ø Growth occurs by successive addition of monomer to limited

number of growing chains

Ø Elementary reaction: initiation, propagation, termination, etc

Ø The reaction rate and activation energy of every elementary

reaction have relatively larger differences

Ø Reaction system: monomer, polymer, initiator

Ø Monomer consumed relatively slow, but MW increases rapidly

Most addition PZN belong to chain PZN

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 3. PZN PROCESSES (VIII)

Chain PZN

Molecular weight

Step PZN

0 20 40 60 80 100
Conversion %

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 3. PZN PROCESSES (IX)

F Living PZN
For anionic PZN

X X X X

Nu + CH2 C Nu CH2 C Nu CH2 C CH2 C

n
Y Y Y Y

fast initiation slower propagation no termination

Ø Linear increase of MW with conversion

Living PZN
MW & its distribution
Composition
Control molecular characteristics
Microstructure
Architecture

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 3. PZN PROCESSES (X)

Chain PZN

Molecular weight
Living PZN

Step PZN

0 20 40 60 80 100
Conversion %

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 3. PZN PROCESSES (XI)

F Controlled/Living radical PZN

Ø Stable free radical PZN (SFRP) (1993, Geoges)

.O N TEMPO: 2,2,6,6-tetramethylpiperidinoxy

Ø Atom transfer radical PZN (ATRP)

(1995, M. Sawamoto; K. Matyjaszewski)
R–X/CuX/ligand (ex. bipyridine)

Ø Reversible addition-fragmentation transfer radical PZN (RAFT)

(1998, G. Moad)
S

RAFT agent: dithioesters（双硫酯） C R

Z S

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 3. PZN PROCESSES (XII)
Ring-opening PZN (ROP)
O O
F n NH C ROP
NH R C n
R
lactam polyamide
Cyclic monomer Linear polymer

O ROP
F CH2 CH2
CH2CH2O
n

ethylene oxide poly(ethylene oxide) (PEO)

Ø ROPs usually proceed by the chain PZN mechanism

Ø Many ROPs: MW increases linearly with conversion (living PZN)

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 4. NOMENCLATURE OF POLYMERS (I)

Nomenclature

Ø Nomenclature based on source (来源基础命名法)

Ø Nomenclature based on structure (结构基础命名法)

Ø IUPAC nomenclature system (系统命名法)

IUPAC: International Union of Pure and Applied Chemistry

Ø Trade name (商品名)

Ø Abbreviations (英文缩写)

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 4. NOMENCLATURE OF POLYMERS (II)

Vinyl polymers

F Nomenclature based on source (来源基础命名法 )

(1) poly + monomer name

CH 2 CH 2 CH 2CH 2 n polyethylene

CF2 CF2 CF2CF2 polytetrafluoroethylene

n

CH 2 CH CH 2CH polystyrene

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 4. NOMENCLATURE OF POLYMERS (III)
(2) poly (monomer name):
more than one word, or have a letter or number before monomer name

CH2 CH CH2CH poly(acrylic acid)

CO2H CO2H n

CH3 CH3

CH2 C CH2CH poly(α-methylstyrene)

n

CH2 CH CH2CH poly(1-pentene)

CH2CH2CH3 CH2CH2CH3 n

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 4. NOMENCLATURE OF POLYMERS (IV)

F IUPAC nomenclature system (系统命名法)

(1) The smallest structural repeating unit (CRU) is identified.

CRU (constitutional repeating unit) (重复结构单元)

RU: CRU:
CH2CH2 n CH2CH2 CH2

CF2CF2 n CF2CF2 CF2

(2) Substituent groups on the backbone are assigned the lowest possible
numbers.

CH2CH CHCH2
CRU:

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 4. NOMENCLATURE OF POLYMERS (V)

CH2 CH2 CRU: CH2 CH2

C C C C
CH3 H n CH3 H

(3) poly(CRU name)

CH 2CH CH CH 2 poly(1-phenylethylene)

3 4
CH2 CH2 1 2 CH2 CH2
C C C C
CH3 H n CH3 H
cis-poly(1-methyl-1-butene-
1,4-diyl)

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 4. NOMENCLATURE OF POLYMERS (VI)

Polymer structure Source name IUPAC name

CH2CH2 n polyethylene poly(methylene)
CF2CF2 n polytetrafluoroethylene poly(difluoromethylene)
CH3
poly(methyl poly[1-(methoxycarbonyl)-
CH2C
methacrylate) 1-methylethylene]
CO2CH3 n

CH2CH
poly(vinyl acetate) poly(1-acetoxyethylene)
OCCH3
O n

CH2 CH2 cis-1,4-polyisoprene cis-poly(1-methyl-1-butene-

C C
CH3 H n 1,4-diyl)
CH 2CH poly(2-vinylpyridine) poly[1-(2-pyridinyl)ethylene]
N

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 4. NOMENCLATURE OF POLYMERS (VII)

Nonvinyl polymers
F Nomenclature based on source (来源基础命名法)
Cyclic monomer or single monomer :
poly + monomer name or poly + (monomer name)
O O
n NH
NH(CH2)5C n
caprolatam polycaprolactam (or nylon 6)
6

O O
n OCH2CH2C n
O

β-propiolactone Poly(β-propiolactone)
3-propiolactone poly(3-propiolactone)

n HOCH2CH2OH CH 2CH 2O
n
ethylene glycol poly(ethylene glycol) (PEG)

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 4. NOMENCLATURE OF POLYMERS (VIII)

F Nomenclature based on structure (结构基础命名法)

Two different monomer： poly (name of the structural group)
O O
n HOOC COOH + n HOCH2CH2OH
OCH2CH2OC C
n
terephthalic acid ethylene glycol poly(ethylene terephthalate)
PET, polyester
的确良, 涤纶

O O
n H2N(CH2)6NH2 + n HOOC(CH2)4COOH NH(CH2)6NHC(CH2)4C
n
hexamethylene diamine adipic acid poly(hexamethylene adipamide)
Nylon 6,6, polyamide
尼龙 6,6

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 4. NOMENCLATURE OF POLYMERS (IX)

F IUPAC nomenclature system (系统命名法)

(1) The smallest structural repeating unit (CRU) is identified.
Ex., poly(β-propiolactone)

O O O O

OCH2CH2C OCH2CH2C OCH2CH2C OCH2CH2C

O O O

OCH2CH2C n CH2CH2CO n CH2COCH2 n

O O

COCH2CH2 n OCCH2CH2 n

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 4. NOMENCLATURE OF POLYMERS (X)
(2) The order of decreasing priority for heteroatom(s) is
O > S > N > P > C.
O O
OCH2CH2C n OCCH2CH2 n

(3) Substituent groups on the backbone are assigned the lowest

possible numbers.

OCCH2CH2 n

(4) poly(CRU name)

O
poly[oxy(1-oxopropane-1,3-diyl)]
OCCH2CH2 n

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 4. NOMENCLATURE OF POLYMERS (XI)

Polymer structure Source name

Monomer (polyethers) IUPAC name

HOCH2CH2OH
poly(ethylene glycol)
CH2CH2O
n
ethylene glycol poly(oxyethylene)
O
CH2CH2O poly(ethylene oxide)
CH2 CH2 n
ethylene oxide poly(oxyethylene)

CH3CHO
CHO polyacetaldehyde
acetaldehyde CH3 n poly(oxyethylidene)

HCHO polyformaldehyde
CH2O n
formaldehyde poly(oxymethylene)

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 4. NOMENCLATURE OF POLYMERS (XII)

Polymer structure Source or common name

Monomer (polyesters) IUPAC name

O O poly(3-propiolactone)
O
OCH2CH2C poly[oxy(1-oxopropane-1,3-diyl)]
3-propiolactone

O poly(10-decanoate)
HO(CH2)9CO2H
10-hydroxydecanoic acid O(CH2)9C poly[oxy(1-oxodecane-1,10-diyl)]

HOCH2CH2OH O O poly(ethylene terephthalate)

+
OCH2CH2OC C poly(oxyethyleneoxytere-
HO2C CO2H phthaloyl)
terephthalic acid

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 4. NOMENCLATURE OF POLYMERS (XIII)

Polymer structure Source or common name

Monomer (polyamides) IUPAC name

O O poly(caprolactam) or nylon 6
NH
NH(CH2)5C poly[imino(1-oxohexane-1,6-diyl)]
caprolactam

O poly(11-undecanoamide) or nylon 11
H2N(CH2)10CO2H
11-aminoundecanoic acid
NH(CH2)10C poly[imino(1-oxoundecane-1,11-diyl)]

H2N(CH2)6NH2
O O poly(hexamethylene aidpamide)
hexamethylene diamine
+ NH(CH2)6NHC(CH2)4C poly(iminohexane-1,6-diylimino-
HO2C(CH2)4CO2H adipoyl)
adipic acid

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 4. NOMENCLATURE OF POLYMERS (XIII)
Commonly used polymer abbreviations
Acrylonitrile–butadiene–styrene
ABS PF Phenol–formaldehyde polymer
copolymer
EPR (or EPM) Ethylene–propylene rubber PMMA Poly(methyl methacrylate)
HDPE High–density polyethylene PP Polypropylene

LCP Liquid crystal polymers PPO Poly(phenylene oxide)

LDPE Low–density polyethylene PS Polystyrene

LLDPE Linear low–density polyethylene PTFE Polytetrafluoroethylene

Melamine–formaldehyde
MF PVAc Poly(vinyl acetate)
polymer
PAN Polyacrylonitrile PVC Poly(vinyl chloride)

PC Polycarbonate SBR Styrene–butadiene rubber

PEO Poly(ethylene oxide) UF Urea–formaldehyde polymer

PET Poly(ethylene terephthalate) UP Unsaturated polyester

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 4. NOMENCLATURE OF POLYMERS (XIII)

Source or common name:

Simple and convenient
In general, the source or common name
is used for the common polymers.

Abbreviations:
Simple and convenient
The abbreviations are used in journal, articles
and trade.

IUPAC system:
Strict and complicated
The IUPAC system is generally used for
all except the common polymers.

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 5. MOLECULAR WEIGHT (I)
Molecular weight (MW)

Dependence of mechanical strength on polymer MW

Mechanical strength
Critical point or Limitimg value
Entanglement MW Difficult to synthesize & process
5,000 ~ 10,000 C
B

A ³ 1,000
M0 Ms MW

M0 : MW for emerging strength; Ms : MW for saturation strength

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 5. MOLECULAR WEIGHT (II)

Ø The higher the MW, the tougher the polymer

Ø M0 & MS : related to intermolecular forces
Crystalline polymer (M0 and MS ) < amorphous polymer
Polar polymer (M0 and MS ) < non-polar polymer

MW, M0 and MS of commonly used polymers

M0 (×10-4) MS(×10-4) MW (×10-4)
PS 6 30 10 ~ 30
Plastics
HDPE 2.8 – 6 ~ 30
PET 0.8 3.0 1.8 ~ 2.3
Fiber
Nylon 6,6 0.6 2.4 1.2 ~ 1.8
Rubber SBR – – 15 ~ 20

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 5. MOLECULAR WEIGHT (III)

Polymer: in general, the mixtures of molecules

Weight fraction, wx
of different MW

MW

Molecular weight distribution (MWD)

MW was described by average molecular weight

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 5. MOLECULAR WEIGHT (IV)

F Number-average MW (Mn)

Molecular weight: M1, M2, … Mx

Number of molecules : N1, N2, … Nx N = å Nx
Weight of molecules : W1, W2, … Wx

W = å Wx = å M x N x

W å NxM x
Mn = = = å nx M x
å Nx å Nx

Nx
nx = Mole fraction of Mx
å Nx

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 5. MOLECULAR WEIGHT (V)

Methods of measurement:

Ø Colligative properties of solution

¹ Vapor pressure lowering ( < 1 ~ 1.5万)
¹ Freezing point depression ( < 0.1 ~ 1万)
¹ Osmotic pressure ( 2万 ~ 50万)

Ø End group analysis

¹ 1H-NMR
< 2.0万
¹ -COOH/KOH (titration)

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 5. MOLECULAR WEIGHT (VI)

F Weight-average MW (Mw)

å Wx M x å N x M x2
Mw = = = å wx M x
å Wx å NxM x

Wx
wx = Weight fraction of Mx
å Wx

Methods of measurement:

Ø Light scattering method (光散射法) > 5千 ~ 1.0万

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 5. MOLECULAR WEIGHT (VII)

F Viscosity-average MW (Mv)

1/a
éå N x M ax +1 ù
Mv = [
å wx M x ]
a 1/ a = ê
êë å N x M x
ú
úû

α (constant) Dependent on the hydrodynamic volume of polymers

α: Variation with polymer, solvent, temperature

Mark-Houwink equation [h ] = KM va
Intrinsic viscosity
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 5. MOLECULAR WEIGHT (VIII)
Methods of measurement : Viscometer
h t
Relative viscosity h rel = =
h0 t0
Specific viscosity h sp = h rel - 1
h sp
Reduced viscosity h red =
C
ln h rel
Inherent viscosity h inh =
C
capillary
h red ×
×
×
×
[h ] × h inh
Ubbelohde viscometer
× ×
× (乌氏黏度计)

C
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 5. MOLECULAR WEIGHT (IX)

F Molecular weight distribution (MWD)

Weight fraction, wx
Mn lower MW fraction

Mv
Mw higher MW fraction

MW

MWD or polydispersity index (PDI) = M w

Mn
Methods of measurement:
Ø GPC (Gel Permeation Chromatography, 凝胶色谱仪)
Ø MALDI-TOF or MALDI-MS (基质辅助激光解吸离子化质谱)
(matrix-assisted laser desorption ionization mass spectrometry)
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 5. MOLECULAR WEIGHT (X)

F GPC
Injection valve
(loaded onto loop)
Pressure
pump
MWD
.…
.…
.…
.… Sample Column Relative Mn & Mw
injection
Solvent bottle
Detector
Recorder

Solvent : THF, toluene, DMF, chloroform, H2O

UV detector
Detector : RI (refractive index) detector
Viscosity detector

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 5. MOLECULAR WEIGHT (XI)

F MALDI-MS

laser pulse
Polymer + solid matrix Vaporized polymer
with attached metal ions

MWD
Absolute Mn & Mw

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 5. MOLECULAR WEIGHT (XII)

Typical ranges of Mw/Mn in synthetic polymers

Polymer Range

Living polymers 1.01 ~ 1.05

Addition polymer, terminated by coupling 1.5

Addition polymer, terminated by disproportionation 2.0

high conversion vinyl polymers 2~5

branched polymers 20 ~ 50

Condensation polymers 2.0

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 6. MICROSTRUCTURE OF POLYMERS (I)

Positional Isomerism (结构[位置]异构)

R R R R
n CH2 CHR CH2 CH CH2 CH CH2 CH CH CH2
Head tail head tail head tail tail head
head-to-tail tail-to-tail

predominant

Configuration Isomerism (构型异构)

Configuration ?
The different spatial arrangements that cannot change from one to
the other or such a change requires the breaking of chemical bonds
Stereoisomerism (立体异构)
Geometric isomerism (cis-trans isomerism) (几何异构(顺反异构))

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 6. MICROSTRUCTURE OF POLYMERS (II)

F Stereoisomerism
R

CH2 CH
n

H R H R H RH RH R
C C C C C
CH2 CH2 CH2 CH2 CH2 Isotactic (等规)

H RR H H R R HH R
C C C C C
CH2 CH2 CH2 CH2 CH2 Syndiotactic (间规)

H H H RR HH RH R
C C C C C
CH2 CH2 CH2 CH2 CH2 Atactic (无规)

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 6. MICROSTRUCTURE OF POLYMERS (III)

F Geometric Isomerism (cis-trans Isomerism)

n CH2 CH CH CH2 CH2 CH CH CH2 n

1,3-butadiene polybutadiene

CH2 CH2
C C cis-polybutadiene
H H n

CH2 H
C C trans-polybutadiene
H CH2 n

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 7. PHYSICAL STATE OF POLYMERS (I)
Ø Conformation ?
The different arrangements of atoms and substituents of the
polymer chain brought about by rotations about single bonds.

fully
random coil folded chain helical chain
extended chain

For solid polymers:

Crystalline: the ordered regions of polymer chains

Morphology (结晶)
(形态)
Amorphous: the disordered regions of polymer chains
(无定形)

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 7. PHYSICAL STATE OF POLYMERS (II)
Crystalline & Amorphous Behavior

F Fringed-micelle model (缨状微束模型) (1930s)

Crystalline region
Crystallite (微晶)

Amorphous region

Ø Crystallites imbedded in a disordered, amorphous polymer matrix

Ø Polymer molecules pass through several different crystalline region

Crystalline and amorphous regions can be not separated

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 7. PHYSICAL STATE OF POLYMERS (III)
Single crystal:
Crystalline and amorphous regions can be separated
Thickness of lamella : 10 nm
Length of polymer chain > 100 nm

F Folded-chain lamella model (折叠链晶片模型) (1950s)

10nm

Adjacent reentry model Switchboard model

(近邻松散折叠) (跨层折叠)

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 7. PHYSICAL STATE OF POLYMERS (IV)
Thermal Transitions
Crystalline melting temp. (Tm):
the melting temp. of the crystalline domains
Glass transition temp. (Tg):
the temp. at which the glass transition of the amorphous
domains occurs

For semicrystalline polymer (DSC curve)

Crystallization temp. (Tc)

Exothermal

T
Tg Tm

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 7. PHYSICAL STATE OF POLYMERS (V)

F Polymer materials:
Tm : The ceiling temp. of crystalline polymers for application

Tg : The ceiling temp. of amorphous polymers for application

Tm, Tg : Important targets of heat resistance of polymers

F Influence Factor of Tm, Tg :

Tg 1
» (symmetrical molecules)
Tm 2
Molecular symmetry
Tg 2
» (asymmetrical molecules)
Tm 3
Structural rigidity
Secondary attractive forces of polymer chains

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 7. PHYSICAL STATE OF POLYMERS (VI)
Thermal transitions of polymers
Polymer Repeating Unit Tg (oC) Tm (oC)
Polydimethylsiloxane —OSi(CH3)2— -127 -40
Polyethylene —CH2CH2— -125 137
Polyoxymethylene —CH2O— -83 181
Polyisobutylene —CH2C(CH3)2— -73 44
Polypropylene —CH2CH(CH3)— -13 176
Poly(vinyl acetate) —CH2CH(OCOCH3)— 32 -
Poly(ε-caprolactam) —(CH2)5CONH— 40 223
Poly(hexamethylene adipamide) —NH(CH2)6NHCO(CH2)4CO— 50 256
Poly(ethylene terephthalate) —OCH2CH2OOC—Ø—CO— 61 270
Poly(vinyl chloride) —CH2CHCl— 81 273
Polystyrene —CH2CH (C6H5)— 100 250
Poly(methyl methacrylate) —CH2C(CH3)(CO2CH3)— 105 220

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 8. INDUSTYIAL POLYMERS (I)
Plastics, Fibers, Elastomers (rubbers), Coatings, Adhesives

Stress (σ) Rigid plastics

Fiber

Flexible plastics

Elastomer

Strain (ε)

Ø Modulus (E, 弹性模量)

Rigid plastics > Fiber > Flexible plastics > Elastomer

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 8. INDUSTYIAL POLYMERS (II)

F Features of Polymers :
Low density (light weight) (0.83 ~ 2.2 g/cm3)
High specific strength & specific modulus (σ/ρ, E/ρ)
Good processability
Corrosion resistance
Easy coloring
Poor electric & thermal conductivity
Inexpensive price

Synthetic polymers : ~1.5 亿吨 /年 (late 1990’s)

Plastics, Fibers, Elastomers (rubbers), Coatings & Adhesives
56% 18% 11% ~15%

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 8. INDUSTYIAL POLYMERS (III)
Plastics
1980s: the volume of plastics > steel & iron

Commodity plastics high volume, low cost

(通用塑料)
Thermolplastics
higher cost, lower volume
Engineering plastics superior mechanical properties
(工程塑料) greater durability
good heat resistance

Thermosetting plastics Crosslinked polymers

Thermoplastics : Thermosetting plastics ≈ 6 : 1

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 8. INDUSTYIAL POLYMERS (IV)

Commodity Plastics

Type Abbreviation Major Uses

Low-density Packaging film, wire and cable insulation, toys,

LDPE
polyethylene flexible bottles, housewares, coatings

High-density Bottles, drums, pipe, conduit, sheet, film, wire and

HDPE
polyethylene cable insulation
Automobile and appliance parts, furniture, cordage,
Polypropylene PP
webbing, carpeting, film packaging
Construction, rigid pipe, flooring, wire and cable
Poly(vinyl chloride) PVC
insulation, film and sheet
Packaging (foam and film), foam insulation,
Polystyrene PS
appliances, housewares, toys

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 8. INDUSTYIAL POLYMERS (V)

Principal Engineering Plastics

Type Abbreviation Type Abbreviation

Acetal a POM Polyetheretherketone PEEK

Polyamide b — Polyetherimide PEI
Polyamideimide PAI Polyimide PI
Polyarylate Poly(phenylene oxide) PPO

Polybenzimidazole PBI Poly(phenylene sulfide) PPS

Polycarbonate PC Polysulfone —
Polyester c —
a Common name for polyformaldehyde. Abbreviation refers to poly(oxymethylene)
b Principally nylon 6 and 6,6

c Principally poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT)

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 8. INDUSTYIAL POLYMERS (VI)

Principal Thermosetting Plastics

Type Abbreviation Typical Uses
Phenol- Electrical and electronic equipment, automobile
formaldehyde PF parts, utensil handles, plywood adhesives,
particle board binder
Urea- Similar to PF polymers; also treatment of textiles,
UF
formaldehyde coatings
Unsaturated Construction, automobile parts, boat hulls,
polyester UP marine accessories, corrosion-resistant ducting,
pipe, tanks, etc., business equipment
Epoxy Protective coatings, adhesives, electrical and
— electronics applications, industrial flooring,
highway paving materials, composites
Melamine- Similar to UF polymers; decorative panels,
MF
formaldehyde counter and table tops, dinnerware

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 8. INDUSTYIAL POLYMERS (VII)
Fibers
High strength & modulus
Good elongation
Good thermal stability (withstand ironing)
Requirements Spinnability
Dyeability (可染性)
Chemical resistance
Insect & mildew (霉) resistance

Cotton Polysaccharide cellulose

Natural Fibers Wool Protein
Fibers Silk (丝绸) Protein

Synthetic Fibers

Natural fibers : Synthetic fibers ≈ 1 : 1

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 8. INDUSTYIAL POLYMERS (VIII)
Principal Synthetic Fibers
Type Description
Cellulosic
Acetate rayon Cellulose acetate
Viscose rayon Regenerated cellulose
Noncellulosic
Polyester Principally poly(ethylene terephthalate)
Nylon Include 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 fiber)
Acrylic Contain at least 80% acrylonitrile; included are modacrylic
fibers comprising acrylonitrile and about 20% vinyl chloride
or vinylidene chloride

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 8. INDUSTYIAL POLYMERS (IX)
Rubber (Elastomers)
Rubber (橡胶) Naturally occurring polymer
可混用
Elastomers (弹性体) Synthetic polymer

Resilience (回弹性)
Requirements Network structure
Crosslinking Chemical crosslinking
Non-network structure
Physical crosslinking

PBD
PS cluster

Chemical crosslinking Physical crosslinking (SBS)

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 8. INDUSTYIAL POLYMERS (X)
Principal Synthetic Rubber
Type Description
Styrene-butadiene Copolymer of the two monomers in various proportions depending
on properties desired; called SBR
Polybutadiene Consists almost entirely of the cis-1,4-polymer
Ethylene-propylene Often abbreviated EPDM for ethylene-propylene-diene monomer;
made up principally of ethylene and propylene units with small
amounts of a diene to provide unsaturation
Polychloroprene Principally the trans-1,4 polymer, 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
silicon atoms; also called polysiloxane
Urethane Elastomers prepared by linking polyethers through urethane groups

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 8. INDUSTYIAL POLYMERS (XI)
Coatings & Adhesives
F Coatings (涂料)
Paint (色漆) Used for portrait, landscape
Natural varnish (天然清漆) Used for decorative coating
Lacquer (真漆) Cellulose nitrate

Development of synthetic polymers

Synthetic paint, synthetic varnish (醇酸树脂清漆)

Interior latex wall paint Styrene-butadiene copolymer

Recent
Exterior latex paint Poly(vinyl acetate)/poly(acrylic ester)

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 8. INDUSTYIAL POLYMERS (XII)
Coatings & Adhesives
F Adhesives (黏合剂)
Bitumen (沥青)
Natural gum (天然树胶)
Starch
Cellulose nitrate

Development of synthetic polymers

Phenol-formaldehyde (酚醛树脂)
Used for wood industry
Urea-formaldehyde (脲醛树脂)
Epoxy resin (环氧树脂)
Cyanoacrylate (氰基丙烯酸酯)

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 9. HISTORICAL DEVELOPMENT (I)

The concept of large molecules began in the 1920s, while the

application of polymers was earlier than it.

Ø 1839: Vulcanized rubber (硫化橡胶) was discovered by Charles

Goodyear (US)。

Ø 1868: Celluloid (赛璐珞), cellulose nitrate plasticized with camphor,

was prepared by A. Parks (UK)。
(UK)

Ø 1907: First synthetic polymer—phenolic resin (Bakelite, 酚醛树脂)

was synthesized by Baekeland (BE).

Ø 1920: The macromolecular concept was formulated by Hermann

Staudinger. (received the Nobel Prize in 1953)。

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 9. HISTORICAL DEVELOPMENT (II)

Ø 1930s:

¹ Wallace Carothers studied polycondensation reactions,

synthesized nylon 6,6 and polychloroprene.

¹ Many addition polymers were commercialized via free radical

polymerization.
Ex., PVC, PMMA, PS, PVAc, LDPE

¹ The theory about polymer solutions and the methods of

measurement of molecular weight were established.
(Flory received the Nobel Prize in 1974)

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 9. HISTORICAL DEVELOPMENT (III)

Ø 1940s: World War II has promoted the development of polymer

materials, and many important elastomers and plastics were
synthesized.
Ex., SBR (丁苯橡胶), NBR (丁腈橡胶), butyl rubber (丁基橡胶),
PTFE (有机氟材料), PET (涤纶树脂)，ABS

Ø 1950s: The catalysts of coordinate PZN were discovered by

Ziegler and Natta, and HDPE and isotactic PP were synthesized.
(Ziegler and Natta received the Nobel Prize in 1963)

Ø 1956: Michael Szwarc (US) discovered living anionic PZN. This

technique permitted the preparation of narrow MWD and ‘exact’
di- and tri-block copolymers, which pioneered polymer designs.

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 9. HISTORICAL DEVELOPMENT (IV)

Ø The late 1950s ~ 1960s: Many engineering plastics come out.

Ex., POM (聚甲醛)，PC (聚碳酸酯)，Polysulfone (聚砜)，
PPO (聚苯醚)，Polyimide (聚酰亚胺)

Ø After the 1960s: Special polymers and functional polymers were

developed.
¹ Special polymers：
高模量高强度，耐高低温，耐辐射，高频绝缘，半导体等。

¹ Functional polymers：
分离材料(离子交换树脂、分离膜等)，导电高分子，感光高分子，
高分子催化剂，高吸水性树脂，医用高分子，药用高分子，高分子液晶等。

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 9. HISTORICAL DEVELOPMENT (V)

Ø After the 80s: The new PZN methods and polymers with new
structure have constinuously appeared and developed.

¹ New PZN methods：

Living cationic PZN, GTP (基团转移聚合)，living radical PZN
plasma PZN (等离子体聚合)

¹ Polymers with new structure：

Block copolymer，graft copolymer，star polymer，dendrimer，
hyperbranched polymer, etc.

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 Hermann Staudinger (1881—1965)

H.W.
Review exercises : 2, 3, 5, 6, 7, 8, 10

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