Documente Academic
Documente Profesional
Documente Cultură
: Malcolm P. Stevens
Professor of chemistry at the university of Hartfort
OXFORD UNIVERSITY PRESS 3rd Ed.(1999)
POLYMER CHEMISTRY
CONTENTS
PART 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 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 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
POLYMER CHEMISTRY
Fluorinated
environments
phosphazene
elastomer
for
arctic
POLYMER CHEMISTRY
POLYMER CHEMISTRY
POLYMER CHEMISTRY
CH2
CH2
CHCl
Polymer
CH2CH2
CH2CH2
Cl
O
H2C
CH2
CH2CH2O
HOCH2CH2OH
CH2CH2O
O
HO
CO2H
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
POLYMER CHEMISTRY
D. Types of copolymer
-A-B-B-A-B-A-A-B-
-A-A-A-A-B-B-B-B-
Graft copolymer :
-A-A-A-A-A-A-A-A-
B-B-B-B-B-
POLYMER CHEMISTRY
(a) linear(b)branch
(c)network
POLYMER CHEMISTRY
(c)ladder polymer
(e) polyrotaxane
(f) polycatenane
(g) dendrimer
POLYMER CHEMISTRY
POLYMER CHEMISTRY
POLYMER CHEMISTRY
Other examples
1. Polyester from lactone (1.7)
&
(1.7)
O
OH
CO2H
(1.8)
+
H2O
POLYMER CHEMISTRY
Other examples
2. Polyamide from lactam (1.9), and
from -aminocarboxylic acid (1.10)
O
NH
O
NH
(1.9)
O
H 2N
CO2H
NH
+ H2O
(1.10)
POLYMER CHEMISTRY
Other examples
3. Polyurethane from diisocyanate and dialcohol(1.11)
and from diamine and bischloroformate(1.12):
OCN
NCO
HO
R'
OH
O
CNH
NH2 + ClCO
R'
CNH
NHCO
R'
(1.11)
H 2N
OCCl
(1.12)
NHCO
R'
2HCl
POLYMER CHEMISTRY
Other examples
4. Hydrocarbon polymer from ethylene (1.13), and from
,-dibromide (1.14)
CH2
CH2
initiator
BrCH2(CH2)8CH2Br
2Na
(1.13)
CH2CH2
CH2CH2
2NaBr (1.14)
FUNCTIO
NALCHEMISTRY
PO LYMERS LAB
POLYMER
X
O
HO
CO2H
+ H2O
O
H 2N
CO2H
NH
+ H 2O
(1.8)
(1.10)
POLYMER CHEMISTRY
A + B
OCN
NCO + HO
R'
R'
CNH
NHCO
R'
(1.11)
NH2 + ClCO
R'
CNH
OH
O
H 2N
OCCl
(1.12)
NHCO
R'
2HCl
POLYMER CHEMISTRY
nHO2C
CO2H
CO2H
nH2O
nHOCH2CH2OH
COCH2CH2O
(1.3)
(1.4)
2nH2O
POLYMER CHEMISTRY
C. Carothers equation
( NO : number of molecules
N : total molecules after a given reaction period.
NON : The amount reacted
P : The reaction conversion )
NON
P=
NO
Or
N=NO(1P)
1
1-P
Forexample
At98%conversion
DP =
1
1- 0.98
POLYMER CHEMISTRY
(a)
A
B
A
B
A
B
A
B
A
B
A
B
A
B
(b)
A
B
A
B
A
B
A
B
(c)
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
Propagation
RCH2CH2 + CH2=CH2 RCH2CH2CH2CH2
.
POLYMER CHEMISTRY
ChainReaction
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
(CH2)6
O
O
(1.15)
(CH2)6
O
POLYMER CHEMISTRY
CH2N2
BF3
CH2
N2
(1.16
)
POLYMER CHEMISTRY
1.7 Nomenclature
A. Types of Nomenclature
1.7 Nomenclature
POLYMER CHEMISTRY
CH2CH
CO2H
Poly(-methylstyrene)
Poly(1-pentene)
CH3
CH2C
CH2CH
CH2CH2CH3
POLYMER CHEMISTRY
CH2CH
CHCH2
CH2
1,2-addition
1,4-addition
1,4-Poly(1,3-butadiene)
Poly(1-butene-1,4-diyl)
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
O
O
CCH2CH2
oxy 1-oxopropane-1,3-diyl
CH2CH2
terephthaloyl
POLYMER CHEMISTRY
Polymer
repeating unit
Source or
Common Name
O
H2C
CH2
HOCH2CH2OH
CH2CH2O
CH2CH2O
Poly(ethylene glycol)
O
H2N(CH2)6NH2
HO2C(CH2)8CO2H
Poly(ethylene oxide)
IUPAC name
Poly(oxyethylene)
Poly(oxyethylene)
NH(CH2)6NHC(CH2)8C
Poly(hexamethylene
Poly(iminohexanesebacamide) or Nylon6,10 1,6-diyliminosebacoyl)
OCH2CH2O C
C OCH2CH2OC
C
O
CH2
O
NH
CH2
10
C
POLYMER CHEMISTRY
OCH2CH2
OH
-Hydro--hydroxypoly(oxyethylene)
POLYMER CHEMISTRY
1.7.6 Abbreviations
PVC
Poly(vinyl chloride)
Low-density polyethylene
PET
Poly(ethylene terephthalate)
POLYMER CHEMISTRY
b.Styrene-butadiene copolymer
Synthetic rubber, PET
Latex paint
Fiber (polyester)
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
Type
Abbreviation
HDPE
PP
Poly(vinyl chloride)
PVC
Polystyrene
PS
MajorUses
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
Abbreviation
POM
PAI
PBI
PC
PEEK
PEI
PI
PPO
PPS
ChapterWhereDiscussed
C
11
13
13
12
17
12
12
11
11
13
11
11
11
POLYMER CHEMISTRY
Abbreviation
Phenol-formaldehyde
TypicalUses
ChapterWhere
Discussed
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
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
POLYMER CHEMISTRY
Description
Polychloroprene
Principally the trans-1,4polymer, but also some cis-1,4 and 1,2 polymer;
also known as neoprene rubber
Polyisoprene
Nitrile
Butyl
Silicone
Urethane
POLYMER CHEMISTRY
Plastic
Number
Letters
PETEb
Poly(ethylene terephthalate)
HDPE
High-density polyethylene
V or PVC
LDPE
PP
Polypropylene
PS
Polystyrene
OTHER
Poly(vinyl chloride)
Low-density polyethylene
POLYMER CHEMISTRY