Polymer Chemistry
저 자 : Malcolm P. Stevens
Professor of chemistry at the university of Hartfort
OXFORD UNIVERSITY PRESS 3rd Ed.(1999)
POLYMER CHEMISTRY
CONTENTS
PART Ⅰ POLYMER STRUCTURE AND PROPERTIES
1. Basic principles
2. Molecular weight and polymer solutions
3. Chemical structure and polymer morphology
4. Chemical structure and polymer properties
5. Evaluation, characterization, and analysis of polymers
POLYMER CHEMISTRY
CONTENTS
PART Ⅱ VINYL POLYMERS
6. Free radical polymerization
7. Ionic polymerization
8. Vinyl polymerization with complex coordination catalysts
9. Reactions of vinyl polymers
POLYMER CHEMISTRY
CONTENTS
PART Ⅲ NONVINYL POLYMERS
10. Step-reaction and ring-opening polymerization
11. Polyethers, polysulfides, and related polymers
12. Polyesters
13. Polyamides and related polymers
14. Phenol-, urea-, and melamine-formaldehyde polymers
15. Heterocyclic polymers
16. Inorganic and partially inorganic polymers
17. Miscellaneous organic polymers
18. Natural polymers
POLYMER CHEMISTRY
Chapter 1. Basic principles
1.1 Introduction and Historical Development
1.2 Definitions
1.3 Polymerization Processes
1.4 Step-reaction Polymerization
1.5 Chain-reaction Polymerization
1.6 Step-reaction Addition and Chain-reaction Condensation
1.7 Nomenclature
1.8 Industrial Polymers
1.9 Polymer Recycling
POLYMER CHEMISTRY
1.1 Introduction and Historical Development
A. Development of civilization
Stone age → Bronze age → Iron age → Polymer age
B. Application of polymeric materials
ｏ PE milk bottles
ｏ Polyamide bulletproof vests
ｏ Polyurethane artificial heart
ｏ Fluorinated phosphazene elastomer for arctic environments
POLYMER CHEMISTRY
C. The purpose of this book
1. Property difference between polymer and
low molecular weight compound
2. Chemistry of polymer synthesis
3. Chemistry of polymer modification
POLYMER CHEMISTRY
D. Development of polymer chemistry
1833년 : Berzelius, the first use of terminology, polymer
1839년 : Synthesis of polystyrene
1860s : Poly(ethylene glycol), Poly(ethylene succinate)
1900s : Leo Baekeland, synthesis of phenol formaldehyde resin
1920s : Hermann staudinger
Structure of polymer(long-chain molecules), Novel Prize(1953년)
1939년 : W.H. Carothers, Nylon synthesis (Du Pont)
1963년 : Ziegler-Natta, stereoregular polymerization
1974년 : Paul Flory, polymer solution property
1984년 : Bruce Merrifield, solid-phase protein process
POLYMER CHEMISTRY
E. Examples of monomers and polymers
Monomer
CH2
CH2
CH2
CHCl
Polymer
CH2CH2
CH2CH2
Cl
O
H2C
CH2
CH2CH2O
HOCH2CH2OH
CH2CH2O
O
HO
CO2H
O
C
POLYMER CHEMISTRY
1.2 Definitions
A. Acoording to the amount of repeating units
monomer : one unit
oligomer : few
polymer : many (poly – many, mer – part)
telechelic polymer : polymer containing reactive end group
(tele = far, chele = claw)
telechelic oligomer : oligomer containing reactive end group
macromer(=macro monomer) : monomer containing long chain
POLYMER CHEMISTRY
1.2 Definitions
B. DP : Degree of polymerization
The total number of repeating units
contained terminal group
C. The kinds of applied monomers
One kind : Homopolymer
Two kinds : Copolymer
Three kinds : Terpolymer
POLYMER CHEMISTRY
D. Types of copolymer
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-AB-B-B-B-B-
POLYMER CHEMISTRY
E. Representation of polymer types
(a) linear
(b) branch
(c) network
POLYMER CHEMISTRY
F. Representation of polymer architectures
(a) star polymer
(b) comb polymer
(c)ladder polymer
(d) semi- ladder
(or stepladder) polymer
POLYMER CHEMISTRY
F. Representation of polymer architectures
(e) polyrotaxane
(f) polycatenane
(g) dendrimer
POLYMER CHEMISTRY
G. Thermoplastic and thermoset (reaction to temperature)
Thermoplastic : Linear or branched polymer
Thermoset : Network polymer
POLYMER CHEMISTRY
1.3 Polymerization Processes
A. Classification of polymers to be suggested by Carothers
Addition polymers : repeating units and monomers are same
Condensation polymers : repeating units and monomers
are not equal, to be split out small molecule
POLYMER CHEMISTRY
Other examples
1. Polyester from lactone (1.7)
&
from ω-hydroxycarboxylic acid (1.8)
O
O
O
C
O
R
(1.7)
C
R
O
OH
R
CO2H
O
R
C
(1.8)
+
H2O
POLYMER CHEMISTRY
Other examples
2. Polyamide from lactam (1.9), and
from ω-aminocarboxylic acid (1.10)
O
NH
C
O
NH
R
(1.9)
C
R
O
H2N
R
CO2H
NH
R
C
+ H2O
(1.10)
POLYMER CHEMISTRY
Other examples
3. Polyurethane from diisocyanate and dialcohol(1.11)
and from diamine and bischloroformate(1.12):
OCN
R
NCO
+
HO
R'
OH
O
CNH
R
NH 2 + ClCO
R'
O
CNH
R
NHCO
R'
(1.11)
O
O
O
H2N
O
OCCl
(1.12)
O
R
NHCO
R'
O
+
2HCl
POLYMER CHEMISTRY
Other examples
4. Hydrocarbon polymer from ethylene (1.13), and from
α,ω-dibromide (1.14)
CH2
CH2
initiator
BrCH2(CH2)8CH2Br
(1.13)
CH2CH2
2Na
CH2CH2
+
5
2NaBr (1.14)
FUNCTIONAL
POLYMERS LAB
POLYMER CHEMISTRY
1.3 Polymerization Processes
B. Modern classification of polymerization according to
polymerization mechanism
Step growth polymerization : Polymers build up stepwise
Chain growth polymerization : Addition polymerization
molecular weights increase successively,
one by one monomer
Ring-opening polymerization may be either step
or chain reaction
POLYMER CHEMISTRY
1.4 Step-reaction Polymerization
A. Monomer to have difunctional group
1. One having both reactive functional groups in one molecule
A
R
B
R
X
O
HO
R
CO2H
O
R
C
+ H2O
(1.8)
O
H2N
R
CO2H
NH
R
C
+ H2O
(1.10)
POLYMER CHEMISTRY
2. Other having two difunctional monomers
R'
A
R
A + B
OCN
R
NCO + HO
R'
R'
O
CNH
NHCO
R'
O
X
R
(1.11)
O
O
NH2 + ClCO
R'
O
CNH
R
X
OH
O
H2N
R
B
OCCl
(1.12)
O
R
NHCO
R'
O
+
2HCl
POLYMER CHEMISTRY
B. Reaction : Condensation reaction using functional group
Example - Polyesterification
O
n HO
nHO2C
CO2H
O
C
+
nH2O
(1.3)
n
CO2H
+
nHOCH2CH2OH
O
O
C
COCH2CH2O
(1.4)
n
+
2nH2O
POLYMER CHEMISTRY
C. Carothers equation
( NO : number of molecules
N : total molecules after a given reaction period.
NO – N : The amount reacted
P : The reaction conversion )
P=
NO
N
Or
NO
N = NO(1 P)
( DP is the average number of repeating units of all molecules present)
DP = NO/N
DP =
1
1-P
For example
At 98% conversion
DP =
1
1- 0.98
POLYMER CHEMISTRY
(A) Unreacted monomer
A
A
A
A
A
A
A
A
A
A
A
A
(a)
B
B
B
B
B
B
B
B
B
B
B
B
(B) 50% reacted, DP = 1.3
A
(b)
A
B
A
B
A
B
A
A
B
B
A
A
A
A
A
A
B
B
B
B
B
B
B
A
A
A
A
A
A
A
(C) 75% reacted, DP = 1.7
A
(c)
A
B
A
B
A
B
A
B
B
B
B
B
B
B
B
B
(D) 100% reacted, DP = 3
A
(d)
A
B
A
B
A
B
A
A
B
B
A
B
A
B
A
B
A
B
A
B
A
B
B
1.5 Chain-reaction Polymerization
A. Monomer : vinyl monomer
χCH2=CH2
B. Reaction : Addition reaction initiated by active species
C. Mechanism :
Initiation
R + CH2=CH2 → RCH2CH2
.
.
Propagation
RCH2CH2 + CH2=CH2 → RCH2CH2CH2CH2
.
.
POLYMER CHEMISTRY
TABLE 1.1 Comparison of Step-Reaction and
Chain-Reaction Polymerization
Step Reaction
Growth occurs throughout matrix by
reaction between monomers, oligomers,
and polymers
DPa low to moderate
Monomer consumed rapidly while
molecular weight increases slowly
No initiator needed; same reaction
mechanism throughout
Chain Reaction
Growth occurs by successive addition of
monomer units to limited number of
growing chains
DP can be very high
Monomer consumed relatively slowly, but
molecular weight increases rapidly
Initiation and propagation mechanisms different
Usually chain-terminating step involved
Polymerizaion rate increases initially as
No termination step; end groups still reactive
initiator units generated; remains relatively
Polymerization rate decreases steadily as
constant until monomer depleted
functional groups consumed
aDP,
average degree of polymerization.
1.6 Step-reaction Addition and
Chain-reaction Condensation
A. Step-reaction Addition.
O
(CH2)6
+
O
O
(1.15)
(CH2)6
O
POLYMER CHEMISTRY
1.6 Step-reaction Addition and
Chain-reaction Condensation
B. Chain-reaction Condensation
CH2N2
BF3
CH2
+
N2
(1.16)
POLYMER CHEMISTRY
1.7 Nomenclature
A. Types of Nomenclature
a. Source name : to be based on names of corresponding monomer
Polyethylene, Poly(vinyl chloride), Poly(ethylene oxide)
b. IUPAC name : to be based on CRU, systematic name
Poly(methylene), Poly(1-chloroethylene), Poly(oxyethylene)
c. Functional group name :
Acoording to name of functional group in the polymer backbone
Polyamide, Polyester
POLYMER CHEMISTRY
1.7 Nomenclature
d. Trade name : The commercial names by manufacturer Teflon, Nylon
e. Abbreviation name : PVC, PET
f. Complex and Network polymer : Phenol-formaldehyde polymer
g. Vinyl polymer : Polyolefin
POLYMER CHEMISTRY
1.7.1 Vinyl polymers
A. Vinyl polymers
a. Source name : Polystyrene, Poly(acrylic acid),
Poly(α-methyl styrene), Poly(1-pentene)
b. IUPAC name : Poly(1-phenylethylene), Poly(1-carboxylatoethylene)
Poly(1-methyl-1-phenylethylene), Poly(1-propylethylene)
Polystyrene
Poly(acrylic acid)
CH 2CH
CH2CH
CO2H
Poly(α-methylstyrene)
Poly(1-pentene)
CH 3
CH 2C
CH2CH
CH2CH2CH3
POLYMER CHEMISTRY
1.7.1 Vinyl polymers
B. Diene monomers
CH2CH
HC
CH2CH
CHCH2
CH2
1,2-addition
1,4-addition
Source name : 1,2-Poly(1,3-butadiene) 1,4-Poly(1,3-butadiene)
IUPAC name : Poly(1-vinylethylene)
Poly(1-butene-1,4-diyl)
cf) Table 1.2
POLYMER CHEMISTRY
1.7.2 Vinyl copolymer
Systematic
Poly[styrene-co-(methyl methacrylate)]
Poly[styrene-alt-(methyl methacrylate)]
Polystyrene-block-poly(methyl methacrylate)
Polystyrene-graft-poly(methyl methacrylate)
Concise
Copoly(styrene/methyl methacrylate)
Alt-copoly(styrene/methyl methacrylate)
Block-copoly(styrene/methyl methacrylate)
Graft-copoly(styrene/methyl methacrylate)
POLYMER CHEMISTRY
1.7.3 Nonvinyl Polymers
O
O
CCH2CH2
oxy 1-oxopropane-1,3-diyl
O
CH2CH2
O
oxy ethylene oxy
C
C
terephthaloyl
POLYMER CHEMISTRY
* Representative Nomenclature of Nonvinyl Polymers
Monomer
structure
Polymer
repeating unit
Source or
Common Name
IUPAC name
O
H2C
CH2
HOCH2CH2OH
CH2CH2O
CH2CH2O
Poly(ethylene glycol)
O
H2N(CH2)6NH2
HO2C(CH2)8CO2H
Poly(ethylene oxide)
Poly(oxyethylene)
Poly(oxyethylene)
O
NH(CH 2)6NHC(CH2)8C
Poly(hexamethylene
Poly(iminohexanesebacamide) or Nylon6,10 1,6-diyliminosebacoyl)
cf) Table 1.3
POLYMER CHEMISTRY
1.7.4 Nonvinyl copolymers
a. Poly(ethylene terephthalate-co-ethylene isophthalate)
O
O
OCH2CH2O C
O
C OCH2CH2OC
C
O
b. Poly[(6-aminohexanoic acid)-co-(11-aminoundecanoic acid)]
O
NH
CH2
5
C
O
NH
CH2
10
C
POLYMER CHEMISTRY
1.7.5 End Group
H
OCH2CH2
OH
α-Hydro-ω-hydroxypoly(oxyethylene)
POLYMER CHEMISTRY
1.7.6 Abbreviations
PVC
Poly(vinyl chloride)
HDPE High-density polyethylene
LDPE
Low-density polyethylene
PET
Poly(ethylene terephthalate)
POLYMER CHEMISTRY
1.8 Industrial Polymers
a. The world consumption of synthetic polymers
: 150 million metric tons per year.
1) Plastics : 56%
2) Fibers : 18%
3) Synthetic rubber : 11%
4) Coating and Adhesives : 15%
b.Styrene-butadiene copolymer
Synthetic rubber, PET
Fiber (polyester)
Latex paint
Plastic (bottle)
POLYMER CHEMISTRY
1.8.1 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.
POLYMER CHEMISTRY
TABLE 1.4 Commodity Plastic
Type
Abbreviation
Low-density polyethylene LDPE
High-density
Polyethylene
Polypropylene
HDPE
PP
Poly(vinyl chloride)
PVC
Polystyrene
PS
Major Uses
Packaging film, wire and cable insulation,
toys, flexible bottles housewares, coatings
Bottles, drums, pipe, conduit, sheet, film,
wire and cable insulation
Automobile and appliance parts, furniture,
cordage, webbing, carpeting, film packaging
Construction, rigid pipe, flooring, wire
and cable insulation, film and sheet
Packaging (foam and film), foam
insulation appliances, housewares, toys
POLYMER CHEMISTRY
TABLE 1.5 Principal Engineering Plastics
Type
Acetala
Polyamideb
Polyamideimide
Polyarylate
Polybenzimidazole
Poltcarbonate
Polyeseterc
Polyetheretherketone
Polyetherimide
Polyimide
Poly(phenylene oxide)
Poly(phenylene sulfide)
Polysulfoned
Abbreviation
POM
PAI
PBI
PC
PEEK
PEI
PI
PPO
PPS
Chapter
C Where Discussed
11
13
13
12
17
12
12
11
11
13
11
11
11
POLYMER CHEMISTRY
TABLE 1.6 Principal Thermosetting Plastics
Type
Abbreviation
Phenol-formaldehyde
Typical Uses
Chapter Where
Discussed
PF Electrical and electronic equipment,
automobile parts, utensil handles,
plywood adhesives, particle board
binder
Urea-formaldehyde
UF Similar to PF polymer; also
treatment of textiles, coatings
Unsaturated polyester
UP Construction, automobile parts, boat
hulls, 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-formaldehyde MF Similar to UF polymers; decorative
panels, counter and table tops,
dinnerware
14
14
12
11
14
1.8.2 Fibers
1) Cellulosic :
Acetate rayon, Viscose rayon
2) Noncellulosic :
Polyester, Nylon(Nylon6,6, Nylon6, etc)
Olefin
(PP, Copolymer(PVC 85%+PAN and others 15%; vinyon))
3) Acrylic :
Contain at least 80% acrylonitrile
(PAN 80% + PVC and others 20%)
POLYMER CHEMISTRY
1.8.3 Rubber (Elastomers)
1) Natural rubber :
cis-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)
POLYMER CHEMISTRY
TABLE 1.7 Principal Synthetic Fibers
Type
Cellulosic
Acetate rayon
Viscose rayon
Noncellulosic
Polyester
Nylon
Olefin
Acrylic
Description
Cellulose acetate
Regenerated cellulose
Principally poly(ethylene terephthalate)
Includes nylon 66, nylon 6, and a variety of other aliphatic and
aromatic polyamides
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)
Contain at least 80% acrylonitrile; included are modacrylic fibers
comprising acrylonitrile and about 20% vinyl chloride or
vinylidene chloride
1.8.4 Coating and Adhesives
1) Coating :
Lacquer, Vanishes, Paint (Oil or Latex), Latex
2) Adhesives :
Solvent based, Hot melt, Pressure sensitive, etc.
Acrylate, Epoxy, Urethane, Cyanoacrylate
POLYMER CHEMISTRY
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
Ethylenepropylene
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-1,4polymer, but also some cis-1,4 and 1,2 polymer;
also known as neoprene rubber
Polyisoprene
Nitrile
Butyl
Mainly the cis-1,4 polymer; sometimes called “synthetic natural rubber”
Copolymer of acrylonitrile and butadiene, mainly the latter
Copolyner of isobutylene and isoprene, with only small amounts of the
Latter
Contains inorganic backbone of alternating oxygen and methylated silicon
atoms; also called polysiloxane (Chap. 15)
Elastomers prepared by linking polyethers through urethane groups
(Chap. 13)
Silicone
Urethane
1.9 Polymer Recycling
a. Durability of polymer property
1) Advantage : Good materials for use
2) Disadvantage : Environmental problem
b. Treatment of waste polymer : Incinerate,
Landfill, Recycling
ex) Waste Tire : Paving materials
Waste PET : To make monomer ( hydrolysis )
To make polyol ( glycolysis )
POLYMER CHEMISTRY
TABLE 1.9 Plastics Recycling Codea
Number
Letters
Plastic
1
PETEb
Poly(ethylene terephthalate)
2
HDPE
High-density polyethylene
3
V or PVC
4
LDPE
5
PP
Polypropylene
6
PS
Polystyrene
7
OTHER
Poly(vinyl chloride)
Low-density polyethylene
Others or mixed plastics
aAdopted
by the Society of the Plastics lndustry (SPI).
bPET is the more widely accepted abbreviation.
POLYMER CHEMISTRY