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POLYMER CHEMISTRY . 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. Basic principles

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polymer chemistry

POLYMER CHEMISTRY

Polymer Chemistry

저 자 : Malcolm P. Stevens

    Professor of chemistry at the university of Hartfort

OXFORD UNIVERSITY PRESS3rd Ed.(1999)

slide2

POLYMER CHEMISTRY

CONTENTS

PART Ⅰ POLYMER STRUCTURE AND PROPERTIES

  • Basic principles
  • Molecular weight and polymer solutions
  • Chemical structure and polymer morphology
  • Chemical structure and polymer properties
  • Evaluation, characterization, and analysis of polymers
slide3

POLYMER CHEMISTRY

CONTENTS

PART Ⅱ VINYL POLYMERS

  • 6. Free radical polymerization
  • Ionic polymerization
  • Vinyl polymerization with complex coordination catalysts
  • Reactions of vinyl polymers
slide4

POLYMER CHEMISTRY

CONTENTS

PART Ⅲ NONVINYL POLYMERS

  • 10. Step-reaction and ring-opening polymerization
  • 11. Polyethers, polysulfides, and related polymers
  • Polyesters
  • Polyamides and related polymers
  • Phenol-, urea-, and melamine-formaldehyde polymers
  • Heterocyclic polymers
  • Inorganic and partially inorganic polymers
  • Miscellaneous organic polymers
  • Natural polymers
chapter 1 basic principles

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

slide6

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

1.1 Introduction and Historical Development

slide7

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

slide8

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
slide9

Monomer

Polymer

POLYMER CHEMISTRY

E. Examples of monomers and polymers

slide10

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

A. Acoording to the amount of repeating units

slide11

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

1.2 Definitions

slide12

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-A-

B-B-B-B-B-

slide13

linear   (b) branch

(c) network

POLYMER CHEMISTRY

E. Representation of polymer types

slide14

(a) star polymer

(b) comb polymer

(c)ladder polymer

POLYMER CHEMISTRY

F. Representation of polymer architectures

(d) semi- ladder

(or stepladder) polymer

slide15

(f) polycatenane

(e) polyrotaxane

(g) dendrimer

POLYMER CHEMISTRY

F. Representation of polymer architectures

slide16

POLYMER CHEMISTRY

G. Thermoplastic and thermoset (reaction to temperature)

  • Thermoplastic : Linear or branched polymer
  • Thermoset   : Network polymer
slide17

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

slide18

(1.7)

(1.8)

POLYMER CHEMISTRY

Other examples

  • Polyester from lactone (1.7)

&

from ω-hydroxycarboxylic acid (1.8)

slide19

(1.9)

(1.10)

POLYMER CHEMISTRY

Other examples

2. Polyamide from lactam (1.9), and

from ω-aminocarboxylicacid (1.10)

slide20

(1.11)

(1.12)

POLYMER CHEMISTRY

Other examples

3. Polyurethane from diisocyanate and dialcohol(1.11)

and from diamine and bischloroformate(1.12):

slide21

(1.13)

(1.14)

POLYMER CHEMISTRY

Other examples

4. Hydrocarbon polymer from ethylene (1.13), and from α,ω-dibromide (1.14)

slide22

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

1.3 Polymerization Processes

B. Modern classification of polymerization according to

   polymerization mechanism

Step growth polymerization : Polymers build up stepwise

slide23

1. One having both reactive functional groups in one molecule

(1.8)

(1.10)

POLYMER CHEMISTRY

1.4  Step-reaction Polymerization

A. Monomer to have difunctional group

slide24

(1.11)

(1.12)

POLYMER CHEMISTRY

2. Other having two difunctional monomers

slide25

(1.3)

(1.4)

POLYMER CHEMISTRY

B. Reaction : Condensation reaction using functional group

Example - Polyesterification

slide26

( NO: number of molecules

N : total molecules after a given reaction period.

NO – N : The amount reacted

P : The reaction conversion )

NO N

P =

NO

Or

N = NO(1 P)

( DP is the average number of repeating units of all molecules present)

DP = NO/N

1

DP =

1 - P

For example

At 98% conversion

1

DP =

1- 0.98

POLYMER CHEMISTRY

C. Carothers equation

slide27

(A) Unreacted monomer

(B) 50% reacted, DP = 1.3

(C) 75% reacted, DP = 1.7

(D) 100% reacted, DP = 3

slide28

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

1.5 Chain-reaction Polymerization

slide29

Step Reaction

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

initiator units generated; remains relatively

constant until monomer depleted

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

No termination step; end groups still reactive

Polymerization rate decreases steadily as

functional groups consumed

aDP, average degree of polymerization.

TABLE 1.1 Comparison of Step-Reaction and

Chain-Reaction Polymerization

slide30

1.6 Step-reaction Addition and

Chain-reaction Condensation

A. Step-reaction Addition.

(1.15)

POLYMER CHEMISTRY

slide31

POLYMER CHEMISTRY

1.6 Step-reaction Addition and

Chain-reaction Condensation

B. Chain-reaction Condensation

(1.16)

slide32

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

slide33

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

slide34

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)

PolystyrenePoly(acrylic acid)

Poly(α-methylstyrene) 

Poly(1-pentene)

slide35

POLYMER CHEMISTRY

1.7.1 Vinyl polymers

B. Diene monomers

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

slide36

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

1.7.2 Vinyl copolymer

slide37

1-oxopropane-1,3-diyl

oxy

oxy

ethylene

oxy

terephthaloyl

POLYMER CHEMISTRY

1.7.3 Nonvinyl Polymers

slide38

POLYMER CHEMISTRY

* Representative Nomenclature of Nonvinyl Polymers

Monomer          Polymer            Source or          IUPAC name

structure          repeating unit       Common Name

Poly(ethylene oxide)

Poly(oxyethylene)

Poly(ethylene glycol)

Poly(oxyethylene)

Poly(hexamethylene   Poly(iminohexane-

sebacamide) or Nylon6,10  1,6-diyliminosebacoyl)

cf) Table 1.3

slide39

a. Poly(ethylene terephthalate-co-ethylene isophthalate)

b. Poly[(6-aminohexanoic acid)-co-(11-aminoundecanoic acid)]

POLYMER CHEMISTRY

1.7.4 Nonvinyl copolymers

slide40

α-Hydro-ω-hydroxypoly(oxyethylene)

POLYMER CHEMISTRY

1.7.5 End Group

slide41

POLYMER CHEMISTRY

1.7.6 Abbreviations

PVC Poly(vinyl chloride)

HDPE High-density polyethylene

LDPE Low-density polyethylene

PETPoly(ethylene terephthalate)

slide42

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 Industrial Polymers

slide43

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.

slide44

TABLE 1.4 Commodity Plastic

Type

Major Uses

Abbreviation

LDPE

Packaging film, wire and cable insulation,

toys, flexible bottles housewares, coatings

Low-density polyethylene

HDPE

Bottles, drums, pipe, conduit, sheet, film,

wire and cable insulation

High-density

Polyethylene

PP

Automobile and appliance parts, furniture,

cordage, webbing, carpeting, film packaging

Polypropylene

Construction, rigid pipe, flooring, wire

and cable insulation, film and sheet

PVC

Poly(vinyl chloride)

PS

Polystyrene

Packaging (foam and film), foam

insulation appliances, housewares, toys

POLYMER CHEMISTRY

slide45

TABLE 1.5 Principal Engineering Plastics

Type

Abbreviation

Chapter Where Discussed

C

11

13

13

12

17

12

12

11

11

13

11

11

11

POM

PAI

PBI

PC

PEEK

PEI

PI

PPO

PPS

Acetala

Polyamideb

Polyamideimide

Polyarylate

Polybenzimidazole

Poltcarbonate

Polyeseterc

Polyetheretherketone

Polyetherimide

Polyimide

Poly(phenylene oxide)

Poly(phenylene sulfide)

Polysulfoned

POLYMER CHEMISTRY

slide46

TABLE 1.6 Principal Thermosetting Plastics

Chapter Where

Discussed

Type

Abbreviation

Typical Uses

Phenol-formaldehyde

Urea-formaldehyde

Unsaturated polyester

Epoxy

Melamine-formaldehyde

PF

UF

UP

-

MF

Electrical and electronic equipment,

automobile parts, utensil handles,

plywood adhesives, particle board

binder

Similar to PF polymer; also

treatment of textiles, coatings

Construction, automobile parts, boat

hulls, marine accessories,

corrosion-resistant ducting, pipe,

tanks, etc., business equipment

Protective coatings, adhesives,

electrical and electronics

applications, industrial flooring

highway paving materials,

composites

Similar to UF polymers; decorative

panels, counter and table tops,

dinnerware

14

14

12

11

14

slide47

POLYMER CHEMISTRY

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%)        
slide48

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)

slide49

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

slide50

POLYMER CHEMISTRY

  • 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
slide51

TABLE 1.8 Principal Types of Synthetic Rubber

Type

Styrene-butadiene

Polybutadiene

Ethylene-

propylene

Polychloroprene

Polyisoprene

Nitrile

Butyl

Silicone

Urethane

Description

Copolymer of the two monomers in various proportions depending on

properties desired; called SBR for styrene-butadiene rubber

Consists almost entirely of the cis-1,4 polymer

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

Principally the trans-1,4polymer, but also some cis-1,4 and 1,2 polymer;

also known as neoprene rubber

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)

slide52

POLYMER CHEMISTRY

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 )

slide53

POLYMER CHEMISTRY

TABLE 1.9 Plastics Recycling Codea

Plastic

Poly(ethylene terephthalate)

High-density polyethylene

Poly(vinyl chloride)

Low-density polyethylene

Polypropylene

Polystyrene

Others or mixed plastics

Letters

PETEb

HDPEV or PVC

LDPEPPPS OTHER

Number

1

2

3

4

5

6

7

aAdopted by the Society of the Plastics lndustry (SPI).

bPET is the more widely accepted abbreviation.