Polymer Technology

2- Thermosetting Plastics

Thermosets can be defined as those polymers which become irreversibly hard on

heating or by addition of special chemicals.
Thermosets which can be melted by heat and molded or costed under heat, and
pressure, by increasing temperature. It will be chemically change and transfer to
infusible, insoluble material because of cross linking in chain.

The term thermosetting polymer refers to a range of systems which exist initially as
liquids but which, on heating undergo a reaction to from a solid, highly cross linked
matrix to produce a network polymer.

A thermosetting plastic is a polymer that can be caused to undergo cross linking to

produce a network polymer, called a thermo set polymer. Quite commonly,
thermosetting resins are prepared, by intent, in only partially polymerized states
(prepolymers), so that they can be deformed in a heated mold and then hardened by
curing (cross linking).

This hardening involves a chemical change (curing) and hence scrap thermoset cannot
be recycled except as a filler material. The curing process invariably involves a
chemical reaction which connects the linear molecules together to form a single
macromolecule. These connections are known as crosslinks.
Two types

a- solid
b- Viscous liquid
______________________________

Characteristics of thermoset

1- Change irreversible by heat

Or undergo irreversible thermal change

Solid Liquid
Solid
Ø Ø Ø

Solid Ø Viscouse liquid Ø Solid

Physical change chemical change

Ø Ø
1

Cross linked
Polymer Technology

The cross linkage by heating is irreversible process due to formation of new strong
covalent bond .

+ CH2=O -H2O

2- Have free functional group can be crosslinked without heat and pressure to from
three dimensions network

3- Thermo set are insoluble and infusible material

Swell in decomposition

Solvent on heating

4- Have high thermal stability

5- Have good thermal and electrical insulation

So this type of plastic can be used for manufacturing of insulations material

Crosslinked: A difunctional or multifunctional monomer that forms a link between two

polymer chains. Crosslinked polymers have many such crosslinks between neighboring
chains such that a three-dimensional interconnected polymer network result.
The advantages of cross-linking agents:
1. Improve hardness and stiffness.
2. Increase wear and solvent resistance.
3. Increase crazing resistance.
4. Increase brittleness.
5. Increase thermal resistance.
6. Decrease water sorption and solubility.

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Characteristics of Thermoplastic and Thermosetting Polymers

Thermoplastics Thermosets

Good elasticity but depends on the type Very poor elasticity

Easily reshaped on heating Highly intractable crosslink i.e cannot be

remoulded

Weak attractive forces between chains Stronger attractive forces between chains

They are soluble in organic solvents Not soluble in organic compounds

Super abrasion and dimensional stability Better flexural and input resistance

They are flexible and not rigid They are not flexible but rigid because of
network structure formed by cross-linking

Softens without chemical change when Undergoes irreversible change which

heated causes it to harden or set

Properties of Thermosetting Polymers

Thermosetting polymers have a cross-linked 3D structure. This structure inherently
provides these polymers higher strength and breakage resistance. Some of the physical
and chemical properties are also dependent on the components which are used to create
the polymer. We list down some key properties below:
1- Thermosetting plastics are resistant to heat. But when very high heat is applied,
they decompose before reaching melting point.
2- These are generally brittle in nature, because of loss of elasticity upon heating.
3- Once moulded or cured, these cannot be re-shaped by application of heat.
4- The density of thermoset is dependent on constituent components used to create
the polymer.
5- Thermosets are generally resistant to chemical attacks.

Uses of Thermosetting Polymers

As mentioned above, thermosets have some unique properties which make them highly
useful for some of our day-to-day needs. Some of the common uses of thermosetting
polymers are:
- These are used to produce permanent parts for a wide range of industries.
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- Thermosets are used to produce electrical goods and components, including
insulators and panels.
- These are used to produce construction equipment panels.
- Because they are heat resistant, they are used to produce heat shields.
- In automobiles, thermosets are used to produce brake pistons.
- These are used in multiple agricultural equipment including feeding troughs and
motors.

Advantages of Thermosets
The use of thermoset plastics has a number of advantages. Unlike thermoplastics, they
retain their strength and shape even when heated. This makes thermosetting plastics
well-suited to the production of permanent components and large, solid shapes.
Additionally, these components have excellent strength attributes (although they are
brittle), and will not lose significant strength when exposed to higher operating
temperatures.

Thermosets plastics have gained in popularity among manufacturers, who have

switched to their use as a lower cost replacement for metal components.
The benefits that thermoset plastics can offer over their metal counterparts include:
Available molded-in tolerances
Choice of color and surface finishes
High strength-to-weight ratio and performance
Outstanding dielectric strength
Low thermal conductivity and microwave transparency
Resistance to corrosion effects and water
Lower tooling/set-up costs
Reduced production costs over fabrication using metals

Disadvantages of Thermosets
There are certain disadvantages to the use of thermosets whereas the material properties
are not as developed as those of thermoplastics.
The low initial viscosity of materials results in flash and the need for secondary
operations. Also, low tensile strength and ductility tend to result in parts that require
designs with thick walls. The compounds used in thermosets are reactive systems,
which can impact the useful shelf life. Batch processes may exhibit greater variation and
less consistency from lot-to-lot. High levels of some filler in the materials may result in
excessive tool wear. The product quality is dependent upon the degree of crosslinking
established during the molding cycle.

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Polymer Technology

Type of thermosetting

e.x ;- phenol formaldehyde

- Phenol Resins urea formaldehyde

melamine formaldehyde

- Epoxy Resins
- Unsaturated polyester
- Poly urethane

Phenol Resins :- are the

first synthetic resins, its old polymer That are prepared from the condensation of phenol
with formaldehyde and it is called phenol formaldehyde Resin , and commercially
called Baklites

typically the phenol is phenol itself and the aldenyde have been used to produce
phenolic resins specific properties such as reactivity and flexibility . The rarity of
phenolic resins available is quite large as the ratio of pnenol to aldehyde . the reaction
temperature and the catalyst selected can be raried . Phenolic resins Fall into two broad
classes :- among the different phenolic resins

1. Novolac resins.

2. Resole resins.
OH HO

O
H
+
‫حامضي‬ ( )
+ H C H
-
or OH

________________________

Characteristics of Phenol Resins ;-

- advantage
1- Stiffness
2- Good electrical insulation
3- Creep resistance

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4- Dimensional Stability
5- Low smoke emission
6- Low cost 7- Good mechanical properties
Disadvantage
1- Brittle
2- Low flexibility
3- Poor alkaline resistance
4- Dark colors
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Preparation of Phenol Resins;- (resinification )
Phenol-formaldehyde resins are normally prepared by two different methods
Two ways used for this Preparation
A - Preparation of Resoles
By reaction of phenol with excess of formaldehyde using base as catalyst . the mole
ratio of phenol to formaldehyde is lesser than one and under basic condition the
produced is resole
One involves a base catalyst with an excess of formaldehyde over phenol . the initially
formed product ( called a resole ) can be cured to a thermosetting polymer simply by
heating ; as such , it constitutes a one-component system .

Phenol + CH2=O Resole Reslite Restes

Ø Ø Ø

-H2O -H2O
OH
Reactions

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Polymer Technology
OH -
- O O O
OH
_ _
NaOH
PH > 10

O O
-
CH 2 O O
H H C H +
form aldeyhade
_

O-
CH 2 OH O
O CH 2 OH
+ H C H

M ethylot -
O CH 2 H

-
- O
O
O
CH 2 OH CH 2 OH
HO CH 2
H C H +

CH 2 OH H2C OH

heat

OH HO OH
HO CH 2 CH 2 CH 2
CH 2 OH

CH 2 OH H2C CH 2 OH

CH 2 CH 2
HO OH Resole

2- Preparation of Novolac

Two stage , using acidic catalysts and excess of phenol

Using acidic medium with excess of phenol formation of viscous liquid and of low
M.wt which is heat un reactive called Novolac .

Phenol–formaldehyde prepolymers, referred to as novolacs, are obtained by using a

ratio of formaldehyde to phenol of 0.75–0.85 : 1, sometimes lower. Since the reaction
system is starved for formaldehyde, only low molecular weight polymers can be formed
and there is a much narrower range of products compared to the resoles. The reaction is

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Polymer Technology
accomplished by heating for 2–4 h at or near reflux temperature in the presence of an
acid catalyst.

• The reaction between phenol and formaldehyde is exothermic. Therefore the

temperature must be controlled to prevent the build-up of heat, particularly during
the early stages of reaction. When formalin is used, water provides a medium for
heat dissipation.

Oxalic and sulfuric acids are used in amounts of 1–2 and <1 part, respectively, per 100
parts phenol.

Which is can't cross linked because of the absence of methalol groups ( -CH2OH ) so the
cross linking done by using a cross linkage agent like Hexamethylene tetr aiamine.

Reaction :-
O +
H
+
H C H CH2 OH
PH < 3

OH
OH OH
CH 2 OH CH 2 OH
+ heat
+ CH2 OH H +
+ H
(1)

OH HO
OH OH
HO CH 2 CH 2
+ +
+ H2 O + H

exess of phenol +

OH
CH 2 OH

(1)

OH HO OH
CH 2 CH 2

H2C
contai n more than 10 ring of phenol

M.wt > 1000

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Polymer Technology

Resole Novolac

1- One step Two step

2- Base catalyst Acidic catalyst

3- Excess formaldehyde Excess phenol

4- Heat reactive Non Heat reactive

5- Low aromatic content High aromatic content

Easily crosslinkage (by heat) Should be then is crosslinkage

agents

2- Urea - formaldehyde Resins :-

The first mention of a product obtained by the reaction of urea with formaldehyde was
in 1884 . It was not until 1920 . however , that a gzecho - Slovakian John , was granted
the first patent in this field .. Three years later , other patent issued to the Viennese
chemist , pollak , served as the basis for commercial development of a fransparent "
oraganic glass " ( pollopus ) .The actual development of asuccessful pure urea
formaldehyde molding powder was the result of an investigation at mellon in stiute ,
beginning in 1928 , for and

It uses plastic which was light in color a which could be used to replace the heavy
enamel cast - iron frames of scales .

NH3 + CO2 → H2N – CO – NH2

O O O O
+
H2N C NH2 + H C H H2N C NH CH 2 OH 2 + HO CH 2 NH C NH CH 2 OH

O O
+ +
H2N C NH CH2 OH2 H2N C N CH2 + H3O

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Polymer Technology
O
O H2N C
N CH 2 O
3 H2N C N C H2 H2C N C NH2
N CH 2
H2N C
O

O O O O

~ HN C N N C NH CH 2 NH C N N C ~
NH

N N

C O
C O
NH ~
NH ~

3- Melamine - formaldehyde Resins

Aromatic compound & heterocyclic compound was obtain for cyan amide

Although melamine has been known for more than acentury , only recently has this
compound been obtained in good yield commercially it appeared on the American
market in 1939»

calcium carbide is first made from lime and coke in an electric furnace using
asmothered electric are :-

3C +CaO ∆ 2000C CaC2 + CO

The second step is exothermic, but requires external application of heat to raise a part
of the charge to the initiation temperature ( over 900 C )
0
CaC + N2 1000 C CaCN2 + C

CaCN2 + H2SO4 → CaSO4 + H2N – C ≡ N

N
H2N NH2
heat O
3 H2N C N
N
N
+ H C H
excess
NH2

N
2 ( HO CH 2 ) NH NH ( CH 2 OH ) 2

N
N

HN ( CH 2 OH ) 2

pol ymer

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Polymer Technology

Fluxes , such as calcium chloride or fluoride , are added to increase the rate of reaction
or cause into proceed at lower temperature melamine , like urea , reacts with
formaldehyde under neutral or slightly alkaline condition to give methyol melamine .

Stiffness higher than urea formaldehyde and more resistance of moisture.

It is very hard and tough. It has assumed great importance these days particularly in
making crockery. They do not break even when dropped from a height.

4 - Aniline – Formaldehyde Resins: -

The foregoing amino lasts are not amine but are amides or midines . True amine
,such as The aniline is condensation react with formaldehyde ,but the process of
resinfication is fundamentally different a number of commercial plastics of limited
importance are based on the condensation of aniline and formaldehyde .

This condensation , like that of phenol and formaldehyde ,depends upon the PH of the
reaction mixture and the aniline formaldehyde ratio . neutral or slightly acid conditions
, formaldehyde reacts with amino group only .

These Reaction are summarized by the following chart :-

H2N HN ( CH 2 OH ) 2
O
+
H C H

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Polymer Technology
of phenolic Resin :-

1- molded products

2- Laminates of cellulose papers

- Papers

- Wood veneer

For decoration, surfaces for tables , tables, disk (Formicas)

3- adhesives for wood and other surfaces

4- Shell molds 5- Electrical insulators

6- Thermal insulator

7- Coating - varnished

- Protective coating

Epoxy Resins

One of Important thermo set polymers , called ( Gold plastic) because of its commercial
importance.

It is a type of polyethers , but it is called epoxy because of containing of the epoxy

groups

Epoxy group

Characteristics Epoxy Resins

1- Toughness

2- Flexibility because of presence of ether group

3- good adhesion ( for glass , metal or rocks )

4- Excellent chemical resistance ( alkaline, solvent )

5- good electrical insulations

6- good dimensional stability ( no creep )

__________________________

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Polymer Technology
Preparation of Epoxy Resins

Generally epoxy prepared from reaction of di or mult alcohol Compounds with

Epichlorohydrine ( EPH ) in basic

Epichlorohydrine ( EPH )

+ HO-R-OH

epoxy resins can be prepared by the reaction of Bisphenol with Epichlorohydrine , in

basic medium at temp. (50-1100C ), producing resin of (340-4000 )M.wt depending the
molar ratio of reactions first product is crosslinkage compound, while final product is
brittle compound
CH3 CH3
105-110 - +
HO C OH + NaOH HO C O -Na
heat
CH3 CH3
Bi sphenol (1 )
+
O
- + -
O Na CH3 O H2C CH CH2 Cl
Cl CH2 CH CH2 O C OCH 2CH CH2 Cl
- HCl
CH3

O O
CH3
H2C CH2 CH2 O C O CH2 HC CH2 + NaCl
CH3
(2 ) exces s form
epichlorohydrine

O OH O
CH3 CH3

H2C [
CH 2 CH 2 O C O CH 2 CH 2 CH 2] nO C O CH 2HC CH 2

CH3 CH3

(3 )

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Polymer Technology
CH3
- +
HO C O -Na +
CH3

(1 )
O
CH3 OH CH3 O

H2C [
CH 2 CH 2 O C O CH 2 CH 2 CH 2]
nO C O CH 2HC CH 2

CH3 CH3

(3 )

- -
O -
CH3 O CH3 O

H2C CH 2 CH 2 O C O CH 2 CH 2 CH 2 O C O CH 2 CH CH 2

CH3 CH3

OH

OH OH CH3
CH3 HO

H2C CH 2 CH 2 O C O CH 2 CH 2 CH 2 O C O CH 2 CH CH 2

CH3 CH3

polym er

The M.wt of produced resin depend upon the molar ratio of the reactant as show in the
following table:-

Molar ratio EPH / BPA Softening point M.wt

2:1 43 451

1:4 84 791

1 : 33 90 802

1 : 25 100 1133

1:2 112 1430

Practically the ratio 1: 4 is good to prepare monomer of two epoxy groups , liquid , and
of M.wt =340

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Types of epoxy resins

There are two main categories of epoxy resins

1- The glycidly epoxies

a- Glycidly-ether
b- Glycidly-ester
c- Glycidly-amine
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Polymer Technology
Prepare by condensation of dihydroxyed compound (diacid, dibase, diamine) and
EPH

2- Non glycidly epoxies

a- Aliphatic epoxiy
b- Cyclo aliphatic epoxiy

Prepare by peroxidation of olifinic double bond

Curing of epoxy resin

Curing is additional polymerization of epoxy resins to produce resin of manufacture

applications like adhesives , coatings , and moldings .

Curing is done by using curing agents or hardeners like amines , carboxylic acids ,
anhydride , and alcohols. The more used are mult amines hardeners

( polyamine ).

cross linked polymer

So for(1) liquid epoxy or viscous epoxy of low M.wt . it can be curried at normal temp.
since the curing is exothermic process , (2) while for high M.wt epoxy curing is done by
heating after dilution by solvents that called post curing .

The curing is done at three stage :-

A- stage B – stage C - stage

un curing practically fully

resin curing curing

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Polymer Technology

Application of epoxy resin

1- Molding products

for - Air craft , Automobile

- Electrical & Electronic

- Encapsulation

2- Protective coating

4- Laminating material

5- Reinforcing resin

6- polymer alloys ( IPN'S ), Polymer modified asphalt ( PMA )

Poly urethane:-

One of the derivative of carbonic acid ( RNH-COOH ) so poly urethanes called

polycarbonate , any polymer that contains a urethane linkage is classified as a
polymerization , The synthesis of polyurethanes is usually presented as proceeding via
the formation of carbamate (urethane) linkages by the reaction of isocyanates and
alcohols:

used for fibers productions , and adhesives, coatings , elastic polymers , foam ( rigid &
flexible ) .

Preparation of P.U ( polyurethane )

Two ways ;-

1- React of diamine with dichloro formate

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Polymer Technology
O O

Cl C OR O C Cl + H2N R' NH2

dichloro formate

O O

+ 2n HCl [ C OR O C HN R' NH ] n

P.U linke

2- reaction of diisocynate with diol

HO- R – OH + n OCN - R' – NCO →

Diol Diisocynate

HO – [-CH2CH2-O-]-H

Poly ethylene glycol

Or ;-
O
O O
HO ( C CH2 O C (CH 2)4 C O ) CH2 CH2 OH

Poly ethyl adabte polyol

TDI = Tolune DiIsocynate

H3C
NCO H3C
OCN NCO

OCN

( 2,4) ( 2,6 )

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Polymer Technology
MDI = Methylene Diphenlyene DiIsocynate

OCN CH2 NCO

if we wish to make thermoplastic linear polymers , we use only diisocyanates . When

thermosets are required , we use a mixture of diisocyanates and tri-or polyisocyanates ,
residues of the latter becoming crosslinks between Chains .

Curing of poly urethane (PU)

1- Produce allphenete flexible PU this process depended on percentage of reaction

+ →
PU excess Allophanate

( flexible PU)

Crosslinkage polyurethane

2- Produce rigid PU

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Polymer Technology

Trimethyol propane
H2C CH CH 2

CH 2 CH 2 CH 2

OH OH OH

sorbitol Hexaol
H2C OH

H C OH
HO C H
H C OH

HO C H
H2C OH polyalcohol

+ →

CH3

O CH OH

HC OH

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Polymer Technology

+ →

P U. Foams

There are two ways to produce PU foams :-

1- Mechanical way

Mixing of the raw materials (TDI and polyalcohol) are transported to the plant by road
tankers. Then the reacting mixture expands rapidly on ejection from the mixer By this
time, the foam is fully hardened. It is cut into 2.2 m long blocks
by an electric cutter mounted on top of the settling machine.

2- Chemical way
By using Blowing agents or foaming agents

Two different types of blowing agents are added to the polymer carbon dioxide, AIBN
( Azo Iso Butyl Nitril )and methylene chloride.
CH3 CH3 CH3

.
H5C2 C O O C C2H5 2 H5C2 C O +

CH3 CH3 0 CH3

120 - 140 C

cumene peroxide

AIBN ( Azo Iso Butyl Nitril )

H O
NCO + H2O HN C OH CO 2 + NH3

unstable
O O
NH3 + NCO
NCO H2N C NH2 H2N NH2

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Polymer Technology

Application of PU
Polyurethane foam is the most widely used flexible foam plastic. It is used to produce a
wide variety of items including thermal insulation and packaging materials, comfort
cushions, bed mattresses, carpet backings and resilient floor coverings.

Type of P U foams

1- Flexible P.U foams

Flexible polyurethane foams are open cell materials that allow free movement of air
between the foam cavities. They are commonly available in density of 13 - 80 kg m-3
TDI and polyalcohol are the basic ingredients for polyurethane foam production. A
range of additives, blowing agents and water are also added.
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Polymer Technology
Prepared reaction of polyester of di alcohol with excess from diisocyanate ( TDI, MDI )
forming flexible foam of partially crosslinked

Water also used to produce CO2 gas to form the foam

Foam density decrease as the amount of H2O increase .

- flexible foams used for

1- insulation

2- Impact reducers

2- Rigid P.U. Foams :-

Hard polyurethane plastic would be formed in the condensation reaction if the reaction
is carried out without blowing agent.
Prepared reaction of mult alcohol with diisocyanate ( TDI, MDI ) forming rigid foam of
crosslinked

Application of flexible foams

Are widely used as insulation in commercial , residential , and industrial settings .

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