PHENOL FORMALDEHYDE

PHENOL FORMALDEHYDE (PF)

HISTORICAL DEVELOPMENT

 Phenol formaldehyde polymers are formed by the reaction product

of phenol, or mixture of phenols, with formaldehyde

 PF resins considered to be the first polymeric products produced

commercially

 In 1872 Von Bayer obtained a colourless non-crystallizing resinous

product from the reaction of phenol with formaldehyde, while he
was investigating phenol based dyes.
 Similar materials in an acidic medium was also reported by ter
Mer, Claus and Trainer, Claisen.
 In 1894 similar material in alkaline pH range was first reported.

 In 1907, Baekeland developed an economical method to convert

these resins into mouldable compositions

 The first commercial phenolic resin plant, Bakelite GmbH, was

started on 25th May 1910 by Rutgerswerke AG at Erkner near
Berlin.

 PF resins are used as moulding powders, laminating resins,

adhesive, binders, surface coatings and impregnants.
 MONOMERS: Phenols

 Cumene process is the most important process and accounts for

more than 95% of phenol capacity.

 In this process liquid propylene, containing some propane is mixed

with benzene and passed through a reaction tower containing
phosphoric acid on kieselguhr as catalyst.

 Pure phenol crystallizes in long colourless needles, which melt at

41o C.
 OTHER PHENOLS
Cresol: Only the m-cresol has the three reactive positions necessary
to give cross-linked resins and as so this is normally the desired
material

Xylenols : Of the six isomers only 3-5-xylenol has the three reactive
positions necessary for cross-linking and thus mixtures with a high
proportion of this isomer are generally used.
 FORMALDEHYDE
 Formaldehyde is produced by dehydrogenation of methanol, over
either an iron oxide/molybdenum oxide catalyst or over a silver
catalyst.

 Because of the hazards in handling mixtures of pure oxygen and

methanol, air is used as the oxidizing agent.

 Oxygen is used to burn the hydrogen by-product

 Formaldehyde is a gas with a boiling point of –21o C. It is usually

supplied a stabilized aqueous solution known as formalin

 Furfural is occasionally used to produce resins with good flow

properties for use in moulding powders.
 TYPES OF PHENOL FORMALDEHYDE RESINS
Novolaks :
 Prepared by reacting phenol with formaldehyde in a molar ratio I : 0.8
under acidic conditions.
 There is a slow reaction of the two reactants to form the Ortho and
para hydroxymethylphenols

 These then rapidly condense to form bis(hydroxyphenyl)methane

(HPM)

 Three possible isomers, 2,4'- and 4, 4'-HPM compounds are the main
products
 These materials will then slowly react with further formaldehyde to
form methylol derivatives which in turn rapidly react with further
phenol to produce higher polynuclear phenols with 5-6 benzene
rings per molecule.

 Novolak resins themselves contain no reactive methylol groups and

do not form cross-linked structures on heating.

 When mixed with compounds capable of forming methylene

bridges, e.g. hexamethylenetetramine or paraformaldehyde, cross-
link on heating to form infusible, 'thermoset' structures
Resols
 Prepared by reacting phenol with excess of formaldehyde in a molar
ratio I : 1.5 - 2 under basic conditions.

 Resulting polynuclear polyalcohols are low molecular weight liquid

with less than two benzene rings per molecule, while a solid resol
will have three to four.

 Heating the resins result in cross-linking via the uncondensed

methylol groups or by more complex mechanisms.

 Resols are referred as one-stage resins since cross-linked products

may be made by adjusting the pH.

 Novolaks on the other hand referred as two-stage resins as it is

necessary to add some agent to enable additional methylene bridges
 RESIN MANUFACTURE
Both novolaks and resols are prepared in similar reactor
Novolak resins : A typical charge ratio would be:
Phenol 100 parts by weight
Formalin 33 % w/w 70 parts by weight
Oxalic Acid 1.5 parts by weight

The end point is checked by

noting the extent of flow of a
heated pellet down a given
slope, melting point,alcohol
solubility, free phenol
content and gelation time
with 10% hexa.
 MANUFACTURE OF RESOL RESINS
 Typical charge for a laboratory-scale preparation would be:

Formalin (40%) 112 cm3 (1.5 moles formaldehyde)

Phenol 94 g (1 mole)

0.88 ammonia 4 cm3

 Reaction is followed by melting point, acetone or alcohol solubility, free

phenol content or loss in, weight on stoving at 135°C.

 Two classes of resol distinguished, water-soluble resins prepared using

caustic soda as catalyst, and spirit-soluble resins catalysed by addition of
ammonia

 Water-soluble resols are used for mechanical grade paper, and in

decorative laminates.

 Spirit-soluble resins have good electrical insulation properties

 CURING OF PHENOLIC RESINS
 Novolaks and resols are soluble and fusible low molecular weight
products

 At temperatures below 160°C cross-linking occurs by phenol

methylol-phenolmethylol and phenolmethylol-phenol condensations

 As these reactions occur at the two ortho and the para positions in
phenol, m-cresol and 3,5-xylenol, cross-linked structures will be formed
 Above 160°C additional cross-linking reactions take place involving
the formation and reaction of quinone methides by condensation of

the ether linkages with the phenolic hydroxyl groups

 It is likely that the quinone methide and related structures formed at

these temperatures account for the dark colour of phenolic

compression mouldings
 PHENOLIC mouldING POWDERS

Phenol-folmaldehyde moulding powder will

contain the following ingredients:

1. Resin.

2. Hardener (with Novolaks).

3. Accelerator.

4. Filler.

5. Lubricant.

6. Pigment.

7. Plasticiser (not always used).

Phenolic Resins: In addition to the selection of phenol used and the
choice between novolak and resol there is a number of further

variations possible in the resin. Eg Phenol/formaldehyde ratio, residual

volatile content

Hardener : Hexa is used almost universally as the hardener, 10 to 15

parts of hexa are used in typical moulding compositions

Accelerator: Basic materials such as lime or magnesium oxide

increase the hardening rate of novolak-hexa compositions

Fillers-Woodflour: Fine sawdust is most commonly used filler. It is not

only an effective diluent for the resin to reduce exotherm and shrinkage,

but it is also cheap and improves the impact strength.

Coconut shell flour: Incorporated into the moulding composition in
large quantities and these results in cheaper mixes than the woodflour

Coconut shell flour-filled mouldings have poor mechanical properties and

hence the filler is generally used in conjunction with woodflour.

Cotton Flack: For better impact strength cotton flock, chopped fabric
or even twisted cord and strings may be incorporated.

The cotton flock-filled compounds have the greatest mouldability but the

lowest shock resistance whilst the twisted cords and strings have the

opposite effect.
Other Fillers: Nylon fibres and fabrics are used to confer strength and
flexibility and glass fibres are used for strength and rigidity.

Asbestos are used for improved heat and chemical resistance and silica,

mica and china clay for low water absorption grades.

Iron-free mica powder is particularly useful for electrical insulation

characteristics

Moulding compositions of enhanced heat resistance are developed by the

use of heat-resisting polymers used in conjunction with asbestos and

other mineral fillers.

Lubricants : Stearic acid and metal stearates such as calcium stearate

are used as lubricants at a rate of 1-3% on the total compound
Pigments: Since the formation of quinone methides and their derivatives

which impart a dark colour to the resin, the range of pigments available is

limited to blacks, browns dark blues, greens, reds and oranges.

Plasticisers : Naphthalene, furfural and dibutyl phthalate are used as

plasticisers or more strictly as flow promoters. They are particularly

useful where powders with a low moulding shrinkage are required.

Typical formulation phenolic moulding composition
 COMPOUNDING OF MOULDING COMPOSITIONS

Dry Process

 Finely ground resin is mixed with the other ingredients for

about 15 minutes in a powder blender.

 This blend is then fed on to a heated two-roll mill. The resin

melts and the powdery mix is fluxed into a leathery hide

 The hide from the mill is then cooled, pulverised with a

hammer-mill and the resulting granules are sieved

 Extrusion compounders such as the Buss Ko-Kneader have

been used for mixing phenolic resins. It is claimed that they
produce a better product and are more economical than mill-
mixers.
Wet Process

 High-shock grades cannot be processed on mills or other

intensive mixers without destroying the essential fibrous
structure of the filler.

 In these cases a wet process is used in which the resin is

dissolved in a suitable solvent, such as industrial methylated
spirits, and blended with the filler and other ingredients in a
dough mixer.

 The resulting wet mix is then laid out on trays and dried in an
oven.
 STRUCTURE AND GENERAL PROPERTIES
On heating, resols either self-cure or cure on addition of catalysts. Novolaks
harden after addition of hexamethylene tetramine.
 High degree of cross-linking of phenolic moulding compounds and the
addition of reinforcements lead to the following properties:
 High strength, stiffness and hardness,
 Low tendency to creep,
 High toughness and low-temperature toughness (depending on the
reinforcement),
 Good heat distortion characteristics,
 Low coefficient of linear expansion,
 High resistance to incandescence,
 High resistance to organic solvents, neutral chemicals, weak acids and
alkaline solutions,
 Not resistant to strong acids and alkaline liquors,
 Resistant to stress crack formation,
 Low flammability.
 Only able to be produced in dark colours.
 Characteristic smell; not permitted for contact with food.
 Properties of Phenol moulding compounds
Property ASTN General Mediu High shock Electrical Acid Minimum Heat
Units purpose m low loss resistanc odour resistan
shock e ce

Specific gravity D 792 - 1.35 1.37 1.40 1.85 1.42 1.38 1.94

Shrinkage - Cm/cm 0.006 0.005 0.002 0.002 0.009 0.007 0.002

Impact strength D 256 J 0.22 0.39 1.08-1.9 0.18 0.18 0.23 0.13

Cross-breaking strength D 790 MPa 80 76 83 76 60 78 60

Tensile strength D 638 MPa 55 48 45 58 43 50 34

Blister temperature - o C 175 170 175 190 185 190 195

Power Factor 800 Hz D 150 - 0.1-0.4 0.1- 0.1-0.5 0.03-0.05 0.03-0.14 0.15-0.3 0.1-0.3
0.35
106 Hz
- 0.03- - - 0.01-0.02 - - -
0.05

Dielectric 800 Hz - 6.0-10.0 5.5-5.7 6.0-10.0 4.0-6.0 5.0-6.0 7.0-9.0 8.0-

constant 106 Hz 16.0
- 4.45-5.6 - - 4.3-5.4 - - -

Dielectric (20o C) kV/cm 58-116 78-106 58-97 106-135 87-116 68-87 97-135
Strength D 149
(90o C)
kV/cm 39-97 29-68 19-58 97-135 87-106 29-58 78-116

Water absorption 24h 23oC D 570 mg 45-6 30-50 50-100 2-6 15-25 45-70 3-8

Volume resistivity D 257 Ohm 1012 - 1012 - 1011.5 - 1013.5 - 1013.5 - 1012 - 1011-
cm 1014 1014 1013.5 1016 1015 1013.5 1014
PHYSICAL PROPERTIES
Mechanical and Thermal Properties

 Mechanical and thermal properties are strongly dependent on the

type of filler used.

 Retention of physical properties at elevated temperature sets

phenolic apart from other plastic materials.

 Phenolic mouldings have good flexural strength retentions in a

wide range of temperatures

 Phenolic moulding compounds filled with asbestos and special

fillers have a higher continuous service temperature range of 250
to 280o C.

 Impact resistance and hardness is a function of filler and resin type

as well as degree of cure.
Electrical properties

 As the mouldings are polar, the electrical insulation properties are

not outstanding but are adequate for many purpose.

 One disadvantage of phenolic compared with aminoplastics and the

alkyd resins is their poor tracking resistance under conditions of
high humidity.
 CHEMICAL PROPERTIES

Resistance to chemicals

 PF materials are readily attached by aqueous sodium hydride

solution but cresol- and xylenol – based resins are more resistant.

 PF mouldings are resistant to acids except 50% sulpuric acid,

formic acid and oxidizing acids

Weathering Resistance

 On continued weathering the phenolic mouldings retain their

properties, however the surface becomes rough and matt

 The yellow-brown self colouration of phenolic moulded materials

darkens on exposure to heat and light.
Resistance to High Energy Radiation

 Phenolic resin is very resistant to radiation.

 The best are the asbestos reinforced moulding compounds

Flammability

 Flammability of PF moulding compounds depends on the basic

substance and the additives

Toxicological Assessment

 If good ventilation is provided,no health risk in the manufacture

and processing of PF moulding compounds

 Utensils made from PF moulding compounds which come into

contact with any type of food or condiments are not permitted
 PROCESSING OF PHENOLIC COMPOUNDS
 Phenolic moulding compounds are processed by compression
moulding, transfer moulding, injection moulding and ram extrusion
with simultaneous application of heat and pressure.

Compression moulding

 Compression moulding yields the strongest product in that there is

less damage to any fibrous filler compared with the other process.

Transfer moulding

 In transfer moulding process, pre-weighed, pre-heated compound is

pressed by a plunger through a gate into the mould

Injection moulding

 Injection moulding of phenolic compound is as same as the

thermoplastic materials

 The advanced technique RTC (Runnerless Injection Compression)

method has been developed for fast curing and improved cycle time
 Processing conditions for Phenolic moulding compounds.
Processing condition

Shelf life of compound >2 years

Compression moulding Pelleting

Preparation Preheating , preplasticization
mould temperature 160 to 190 o C
moulding pressure 150 to 180 bar
Curing time per mm 30 to 60 s
(per 40 mils) wall thickness

Transfer moulding
Preparation As by compression moulding
mould temperature 160 to 190 o C
moulding pressure 500 to 2000 bar
Curing time (almost independent of wall 40 to 120 s
thickness)
Remarks preheating promotes plasticization, enables lower injection
pressure to be used
Injection moulding ( not all grades can be
injection moulded)
Preparation (none)
Temperatures
Feed section 65 to 85 o C
Nozzle 85 to 120 o C
Screw 65 to 85 o C
moulding compound 110 to 140 o C
mould 170 to 190 o C
moulding pressure 800 to 2500 bar
Curing time 20 to 80 s
Remarks Feed section of plasticizing cylinder usually cooled.
 Phenolic Laminates
Impregnation plant fitted with vertical drying oven.

 Properties of a phenolic laminate will obviously depend on

 Type of resin used, catalyst, the concentration of methylol groups and
the average molecular weight.
 Properties of the varnish, such as the nature of the solvent and the
viscosity and resin content of the varnish.
 Type of reinforcement.
 Moulding conditions, i.e. moulding pressure, temperature and time.
 AVAILABILITY
 A variety of thermoset phenolics moulding compounds are
available

 Asbestos-free products are available for various applications.

 There are special grades for the electrical and automobile

industries

 Phenolic moulding compounds are supplied as powder, granules

for compression, transfer and injection moulding.

 Fibrous and chipped moulding compounds are also available.

 TYPICAL APPLICATIONS
Appliance
 Broiler end panels, steam irons, coffee-pot bases and handles, knobs,
stick handles, bases, and toaster ends are all made up of PF moulding
compounds.

Automotive

 Phenolics are used in all power-assist break systems because of their

excellent flexural fatigue, heat-resistance, ability to hold close
dimensions, and low manufacturing cost.

 Transmission parts as thrust washers, spacers, and converter reactors

are moulded from heat-resistance phenolic compounds

 Carburetor spacers, . Ignition parts, speedometer housings, solenoid

covers, connectors and numerous other under-the-hood parts are
moulded from heat-resistant and high impact grades of phenolics
UREA FORMALDEHYDE
 UREA AND MELAMINE FORMALDEHYDE RESINS

HISTORICAL DEVELOPMENT

 Among the various amino plastics, Urea and Melamine formaldehyde

resins are the most important commercially

 The interest in amino plastics dates from the publication of a patent

by John in 1918

 In 1926, as a result of work by E.C. Rossiter, moulding powders based

on urea-thiourea-formaldehyde were marketed.

 In 1935 Henkel patented, the production of resins based on melamine.

Today these resins are important in the manufacture of decorative
laminates and in tableware.

 The bulk of the amino resins are used in the woodworking industry
 UREA – FORMALDEHYDE RESINS
Monomer : Urea
 Urea is prepared by the reaction of liquid carbon dioxide and
ammonia in silver-lined autoclaves, at temperature in the range
135-195ºC and pressure of 70-230 atm

 Urea is a white crystalline compound with a melting point of

132.6ºC and is highly soluble in water.

Formaldehyde

 As in the case of phenolic resin, formalin with both high and low
methanol content is used to prepare formaldehyde
 MANUFACTURE OF UREA FORMALDEHYDE RESINS
 Urea-formaldehyde ratios normally employed are in the range 1: 1.3 to
1: 1.5

 Urea-formaldehyde resins are manufactured by a two-stage reaction.

 First stage of resin preparation is to dissolve urea into the 36% w/w
formalin which has been adjusted to a pH of 8 with caustic soda.

 Solution at the end of the first stage process contains urea,

formaldehyde, and mono- and dimethylol urea
Manufacture of Urea and Melamine Formaldehyde Resins
CURING OF UREA-FORMALDEHYDE RESINS

 Product of the first stage, contains unreacted urea and formaldehyde,

is then subjected to acid conditions at elevated temperatures during
the second stage.

 In the first part of the second-stage methylol ureas condense with

each other by reaction of an –CH2OH group of one molecule with an –
NH2 group

 More soluble resins produced on continuation of the reaction contain

pendant methylol groups formed by reactions of the groups with free
formaldehyde - I
 Furthermore the ether linkages on heating may break down to
methylene linkages with the evolution of formaldehyde

 These methylol groups and the methylol groups on the chain ends of
the initial reaction product can then react with other methylol groups
to give either linkages or with amine groups to give methylene
linkages.
+
+

 When reactions II and III occur on average more than twice per
molecule the resin gels, and cross-linking may be considered to have
occurred.
 UREA FORMALDEHYDE mouldING MATERIAL
Compounding Ingredients
Fillers
 Bleached wood pulp is employed for the widest range of bright colours
and in slightly translucent mouldings,
 Woodflour, which is significantly cheaper, also be used.

Pigments

 A wide variety of pigments is now used in U-F moulding compositions

Accelerator
 In order to obtain a sufficient rate of cure at moulding temperatures it
is usual to add about 0.2-2.0% of a 'hardener' (accelerator).
 This functions by decomposing at moulding temperatures to give an
acidic body that will accelerate the cure rate.
 Example :- Ammonium sulphamate, ammonium phenoxyacetate,
ethylene sulphite and trimethyl phosphate.
Stabilizer

 Urea-formaldehyde powders have a limited shelf-life but some

improvement is made by incorporating a stabiliser such as hexamine
into the moulding power

Plasticizers

 Their main virtue is that they enable more highly condensed resins to
be used and thus reduce curing shrinkage whilst maintaining good flow
properties.

 Glyceryl a - tolyl ether (monocresyl glycidyl ether) is often used for this
purpose.

Lubricants

 Metal stearates such as zinc, magnesium or aluminium stearates are

commonly used as lubricants at about I % concentration
 Compounding of moulding Compositions
 Urea-formaldehyde is mixed with the filler (usually with a dry weight
resin-filler ratio of about 2:1) and other ingredients except pigment in a
tough mixer.

 Resulting wet base is then fed to a drier which may be either of the
turbine or rotary type.

 On emerging from the drier the base is hammer-milled and then ball-
milled.

 For densification the powder is heated as it passes along a belt and to

drop the heated powder into the nip of a two-roll mill,

 In this process the material passes directly through the rolls to form a
strip which is then hammer milled to give powder

 More recent processes involve the use of continuous compounders,

such as the Buss Ko-Kneader.
 STRUCTURE AND GENERAL PROPERTIES
 The structure of the pre-condensate is a short chain molecule
combined with CH2 bridges.

 Low cost. The cheaper grades are sometimes lower in weight cost than
the general purposes phenolics. (It is to be noted that urea
formaldehyde have a somewhat higher density).

 Wide colour range.

 They do not impart taste and odour to foodstuffs and beverages with
which they come in contact.

 Good electrical insulation properties with particularly good resistance

to tracking.

 Resistance to continuous heat up to a temperature of 70o C

 TABLE OF PROPERTIES
Urea-formaldehyde Melamine-formaldehyde

Standar
Property d Units
(ASTM) a Transluce
Cellulos Glass Mineral
Cellulose Woodflou Plasticized e filled filled filled
nt
filled Filled

Specific
D 792 -- 1.5-1.6 1.5-1.6 1.5-1.6 ~1.5 1.5-1.55 ~2.0 ~1.8
gravity

Tensile
D 638 MPa 52-80 52-80 48-66 48-69 55-83 41-69 28-41
strength

Impact 0.15-
D 256 ft/lbf 0.20-0.35 0.16-0.35 0.16-0.24 0.14-0.2 0.16-0.23 0.12-0.22
strength 0.24

Cross
breaking D 790 MPa 76-117 76-114 93-107 89-117 89-144 62-96 41-76
strength

Dielectric V/0.001
D 149 120-200 60-180 100-200 70-130 160-240 150-250 200-250
strength in

Volume
D 257 Ohm 1013-1015 1013-1015 1014-1015 -- 109-1010 1015-1016 1015-1016
resistivity

Water
absorption
24 hr. at 24ºC D 570
mg. 50-150 40-170 50-90 50-100 10-50 10-20 7-14
30 min. at
mg. 180-460 250-600 300-450 300-600 40-110 20-35 15-40
100ºC
 PHYSICAL PROPERTIES
Mechanical Properties
 UF and MF are the hardest of all plastic materials.

 UF has a hardness of M-110 to 120 and MF of M-115 to 125 Rockwell

Scale.

 Although they are brittle at normal room temperatures, UF and MF

compounds exhibit very high modulus of elasticity

Thermal Properties
 UF the continuous service temperature is 77ºC and for MF is 99ºC.

 Heat deformation temperature (HDT)under load (1.8 Mpa) is 130ºC for

UF whereas HDT of MF is 183ºC.

Optical Properties
 UF and MF resins are transparent

 Colour possibilities of both the materials are unlimited.

 CHEMICAL PROPERTIES
Resistance to chemicals
 UF resins are resistant to solvents, oils, fats, weak acids and alkalines.

 They are not resistance to strong acids and alkaline solutions, boiling
water, oxidizing and reducing agents.

Weather Resistance
 On immersion in cold water, UF mouldings absorb more water than MF.

 Wood flour filled UF compounds have less weathering effect than

cellulose filled compounds.

Resistance to High Energy Radiation

 Radiation resistance of UF resin is high. In the case of moulding
compounds the nature of the reinforcing materials is the deciding
factor
Flammability

 UF moulded materials burn with a yellow flame and are self-

extinguishing

 The combustion products have a choking smell of amines (fishy) and

formaldehyde.

Toxicological Assessment

 Only special grades of UF are permitted for contact with food.

 Processing conditions for Urea and Melamine Formaldehyde moulding
compounds.
Processing condition Urea Formaldehyde Melamine Formaldehyde

Shelf life of compound <1/2 years <1/2 years

Compression moulding Pelleting Pelleting

Preparation Preheating, preplasticization Preheating, preplasticization
mould temperature 130 to 160 o C 150 to 170 o C
moulding pressure 150 to 800 bar 150 to 800 bar
Curing time per mm
wall thickness 20 to 40 s 20 to 40 s

Transfer moulding
Preparation As by compression moulding As by compression moulding
mould temperature 130 to 160 o C 150 to 170 o C
moulding pressure 500 to 2000 bar 500 to 2000 bar
Curing time (almost independent of wall 30 to 120 s 30 to 120 s
thickness)

Remarks

curing time of the amino plastic is shorter than phenolic

Injection moulding ( not all grades can be

injection moulded)
Preparation (none)

Temperatures
Feed section 70 to 80 o C 65 to 80 o C
Nozzle 95 to 125 o C 90 to 120 o C
Screw 70 to 80 o C 65 to 80 o C
moulding compound 120 to 140 o C 130 to 140 o C
mould 140 to 160 o C 160 to 180 o C
moulding pressure 1000 to 2500 bar 1000 to 2500 bar
Curing time 15 to 80 s 15 to 80 s

Feed section of plasticizing cylinder usually cooled. Screw temperature control only for diameters greater than 50mm
Remarks
 AVAILABILITY
 Although available as fine powders, UF moulding compounds are
mainly available as granules.
TYPICAL APPLICATIONS
Adhesives
 UF resins are used as adhesives for the particle board, plywood and
furniture industries
 Interior decoration panelling is the major end use of the UF particle
board and plywood.
 As gap filling resins by incorporating plasticizers
Moulding compounds
 The first big application of UF resin is the moulding area.
 The bulks of these applications are for plugs, sockets and switches
switch box, plugs, sockets, lamp holders, screw cap for cosmetics, hair
drier housings, table mats, telephone sets and cookware handles etc.