Polymer Chemistry

PhD Halina FalfushynskaPhD Halina Falfushynska

Classification

Protein, Nucleic acid, Polysaccharide

A. Natural

B. Synthetic

PET, Polyurethane , Polyethylene

Application of polymeric materials

PE milk bottles Polyamide bulletproof vests Polyurethane artificial heart Fluorinated phosphazene elastomer for arctic environments

Examples of monomers and polymers

Monomer Polymer

HOCH2CH2OH

HO CO2H

CH2CH2

CH2CH2O

CH2CH2O

O C

O

CH2 CH2

CH2 CHCl CH2CH2

Cl

H2C CH2

O

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

Chain growth polymerization : Addition polymerization         molecular weights increase successively,  one by one monomer Ring-opening polymerization may be either step or chain reaction

Polymerization Processes B. Modern classification of polymerization according to    polymerization mechanism   Step growth polymerization : Polymers build up stepwise

 The total number of repeating units contained terminal group

C. The kinds of applied monomers

B. DP : Degree of polymerization

One kind : Homopolymer

Two kinds : Copolymer

Three kinds : Terpolymer

Definitions

Representation of polymer types

(a) linear   (b) branch

(c) network

(c)ladder polymer

(b) comb polymer (a) star polymer

(d) semi- ladder (or stepladder) polymer

Representation of polymer architectures

Representation of polymer architectures

(f) polycatenane (e) polyrotaxane

(g) dendrimer

The swelling capacity of a polymer

• amount of liquid material that can be absorbed

• Beaker test method• Tea bag test method

diagrammatic representation of part of the polymer network. When water is added to SAP there is a polymer/solvent interaction; hydration and the formation of hydrogen bonds are two of these interactions

Kinetics of polymer swelling

1 – unlimited swelling polymer or/and with low M2 – polymer with high M

Beaker test method

• A small amount of superabsorbent polymer material is taken (0.1g) and it is placed in the beaker.

• 100 ml of doionised water is poured into the beaker.

• After 20 min the swollen polymer was separated by using filter paper

• By weighing the polymer, one can find the swollen capacity of the SAP material.

Degree of swelling

0

0

0

0

V

VV

m

mm

mo – mass of polymer at the beginning,m - mass of polymer at the end

dt

dm

Velocity of swelling

Tea bag test method

• Take 0.1g of SAP material and put the bag suspended over the excess watered beaker

• Note the time 20 min. And weigh the bag • The percentage of swelling:• (w2-w1)/(w1)  % w1= weight of the polymer (Before swelling) w2= weight of the polymer (After swelling)

Abbreviations

PVC Poly(vinyl chloride)

HDPE High-density polyethylene LDPE Low-density polyethylene PET Poly(ethylene terephthalate)

Codes for Plastics

• 1 – PETE – soft drink bottles• 2 – LDPE – plastic bags, toys• 3 – PVC – water pipes• 4 – HDPE – milk jugs • 5 – PP – bottle caps• 6 – PS – styrofoam

1

Commodity Plastic

Type Abbreviation Major Uses

Low-density polyethylene

High-densityPolyethylene

Polypropylene

Poly(vinyl chloride)

Polystyrene

LDPE

HDPE

PP

PVC

PS

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

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)

1.8 Industrial Polymers

Plastics

1) Commodity plastics     LDPE, HDPE, PP, PVC, PS  

2) Engineering plastics     Acetal, Polyamide, Polyamideimide, Polyarylate,     Polybenzimidazole, etc.  

3) Thermosetting plastics  Phenol-formaldehyde, Urea-formaldehyde, Unsaturated polyester, Epoxy, Melamine-formaldehyde    4) Functional plastics     Optics, Biomaterial, etc.

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%)        

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)

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

Principal Types of Synthetic Rubber

Type

Styrene-butadiene

Polybutadiene

Ethylene- propylene

Polychloroprene

PolyisopreneNitrileButyl

Silicone

Urethane

Description

Copolymer of the two monomers in various proportions depending on properties desired; called SBR for styrene-butadiene rubberConsists 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 latterCopolyner of isobutylene and isoprene, with only small amounts of the LatterContains inorganic backbone of alternating oxygen and methylated silicon atoms; also called polysiloxane (Chap. 15)Elastomers prepared by linking polyethers through urethane groups (Chap. 13)

27

You are made of biopolymer

R group varies one unit to the next

N

H

R

O

n

H

28

The 4 levels of structure

• Primary: the sequence of the amino acids

• Secondary: helix, coil or random sheet (and a few others)

• Tertiary: folding of the unit, including –S-S- bridges

• Quaternary: how the blobs assemble

The 4 levels of structure

31

Biopolymers: Nucleic Acids

RNA DNA

CH2

O

PO

OH

O

OCH2

O

OH

PO O

OH

OCH2

O

PO O

OH

O

OPO

O

O

CH2

O

PO O

OH

O

OH

OH

N N

O

O

HU

N

N

N

N

NH

N N

O

NH2

OH

N

N

N

N

O

NH2

A

C

G

Ribose sugar Base

NN

NN

O

OP

O

O

OH

CH2

O

O

OPO

OH

CH2

O

O

OPO

OH

CH2

O

O

OPO

OH

CH2

O

PO O

O

N

N

CH3 O

O

H

N

NO

NH

H

N

N

NH

H

NN

O

NH

H

CH3

N

N

N

NNH

O

H

H

NN

NNH

H

N

N

O

O

H

N

NO

NH

H

O CH2

O

P OO

OH

O

O CH2

O

P O

OH

O

O CH2

O

P O

OH

O

O

O CH2

O

P O

OH

T

G

A

C

A

C

T

G

3'

5'

5'

3'

.....

......

...

........

.........

.....

........

..

.....

....

Microencapsulation

• Micro-encapsulation is a process in which tiny particles or droplets are surrounded by a coating to give small capsules many useful properties. 

• Ionotropic gelation

• In-situ polymerization

• Coacervation-phase separation

CoacervationThe

phenomenon of forming a liquid rich in polymer phase in equilibrium with another liquid phase. 

Mechanism of coacervation

Secondary drop from primary “cluster”

Layering the solution with

coacervates top

Formation of primary droplets

with hydrated macromoleculars