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Maharashtra Institute of Technology, Aurangabad Affiliated to Dr. Babasaheb Ambedkar

Marathwada University Aurangabad Course: Polymeric Materials-I T. Y. B. Tech.
(Plastic and Polymer Engineering)

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Unit-IV Amino Resins A. Structure-properties relationship, properties and application of

Urea Formaldehyde Resins B. Structure-properties relationship, properties and
application of Melamine Formaldehyde Resins References: Plastics Materials,
J.A.Brydson, Seventh Edition, Butterworth- Heinemann PLASTICS MATERIALS AND
PROCESSES -A Concise Encyclopedia, Charles A. Harper, Edward M. Petrie, Wiley-
Interscience Basic Urea- Formaldehyde Resin Chemistry, Zuzana Salkova, Buildin g and
Industrial Mat Spring Meeting, Savamah 2010, Slide nos — 1 to 30

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UF Resins Urea-formaldehyde resins find numerous applications in adhesive, textile

finishing and moulded plastic industries. These resins came into prominence, since they
possess such desirable characteristics as freedom from colour, good clarity and adhesive
quality. Like phenolic resins, urea-formaldehyde resins are, in the finished product
crosslinked, insoluble and infusible materials. A low molecular weight resin is first
formed which is crosslinked in the final fabrication process. Compared to phenolic resins,
urea-formaldehyde products are cheaper, light in colour, odourless and have better
resistance to electrical tracking, but have inferior heat resistance and higher water
absorption. Companies manufacturing urea-formaldehyde resins include American
Cyanamid, Reichhold Chemicals, and Allied Corp.

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UF Resins Urea-formaldehyde (UF) resins are the main binders for wood composite
boards, such as particleboards, fibreboards, or hardwood plywood. In the use of UF
resins, water solubility, good adhesion, high curing rate, and low cost are the attractive
properties. low water resistance and emission of Their drawbacks are formaldehyde from
wood boards, resulting from the low stability of the amino- methylene bond. The key
parameter in the decrease of formaldehyde emission is lowering the formaldehyde/urea
(F/U) ratio in the synthesis of UF resins to 1.05. This leads to a reduction in the content
of crosslinking groups in cured UF resins, lowering the strength and water resistance of
adhesive joints in boards. Ref: Structure formation in urea-formaldehyde resin synthesis,
Peep Christjansona, Tönis Pehk, and Kadri Siimer, Proc. Estonian Acad. Sci. Chem.,
2006, 55, 4, 212—225

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 Urea Formaldehvde Resin Po»der: UF Resins Urea-formaldehyde, also known as urea-
methanal, named for its common synthesis pathway and structure, is a resin/plastic, made
from urea and formaldehyde heated in the presence of a mild base such as ammonia.
Urea-formaldehyde is everywhere and used in many manufacturing processes due to its
useful properties. Examples include decorative laminates, textiles, paper, foundry sand
molds, fabrics, wrinkle resistant cotton blends, rayon, corduroy, etc. It is also used as an
adhesive for wood and other materials like MDF.

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UF / MF RESINS : BASIC PLANT CONFIGURATION & APPLICATIONS URU

UFRESIN n.macutD 230," Em NELAWXE URAWNE lynfGUTED FACED 30 utu.wxt
75 WATER AX) FIRE n.tnQEU.tD coxnxwr, 12 Ref:
http://atec.co.in/ProcessTechnologies_subd84b.html?val=11

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UF- Resins o H2N NH2 3 H2C=O repeat heat _ H20 O HO N N —H20 o HO N N HO o

o 1 urea o HO*AN HO cross-linked resin Reference:

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Addition reaction NH2 UF- Resins- Mechanism — I —CHOH H CH20H NH2 NH2 urea
H N formaldehyde monomethylolurea Polycondensation reaction • by ether links —N—
CH20f{ - c=o NH2 • by methylene links -...-..-N-........-.H.. HO------CH2-...-.— — NH2
NH2 NH2 dimethylolurea NH2 • H20 NH2 NH2 NH2

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UF Resins The resinification process for urea formaldehyde occurs in two main stages,
addition or methylolation and condensation. The ratio of mono to dimethylol compounds
will depend on the urea-to-formaldehyde ratio and it is important that there should be
enough formaldehyde to allow some dimethylol urea formation. In the methylolation
step, urea and formaldehyde are reacted under controlled conditions using an alkaline
catalyst. Typically, the methylolation step is carried out at a pH of about 8.0. The
methylolation stage usually results in a mixture of methylolated species, monomethylol
urea, and dimethylol urea and trimethylol urea.

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UF Resins If the product of the first stage, which in practice usually also contains
unreacted urea and formaldehyde, is then subjected to acid conditions at elevated
temperatures the following sequence of events is observed during the second stage: (1) A
solution is produced from which, if cooled, a white precipitate would be obtained. (2) As
heating proceeds, the temperature at which precipitation occurs drops progressively until
a stage is reached when the condensation products remain in solution at room
 temperature. (3) With further heating there is an increase in viscosity and the syrup sets to
an insoluble and irreversible gel which eventually converts, with the evolution of water
and formaldehyde to a hard, colourless, transparent and infusible mass.

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NH2CONH2 urea + СН2О + formaldehyde рн=д рн=8 NH2CONHCH20H + снао

HOCH2NHCONHCH20H + снрн NH2CONHCH20H monomethylol urea
НОСНАНСОћЈНСН2ОН dimethylol urea (HOCH2)2NCONHCH20H trimethylol urea

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UF Resins The urea methylolation reaction is controlled such that 1 mole of urea
combines with 2 moles of formaldehyde to yield dimethylol urea predominantly. The
second phase of the resinification process involves the condensation of the methylolated
species in the presence of an acid catalyst, which when carried to completion, results in a
fully cured, infusible resin with methylene linkages. The condensation reaction proceeds
to a predetermined end point, and the resin intermediate is cooled. The resin intermediate
is stabilized by adjusting the pH to about 7.0 to 8.0. The condensation of the methylolated
species is equivalent to 2 moles of urea reacting with 1 mole of formaldehyde to form
urea-formaldehyde resin.

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The reaction between urea and formaldehyde is divided into two stages. The alkaline
condensation to form mono-, di-, and trimethylolureas. (Tetramethylolurea has never
been isolated.) The second stage is the acid condensation of the methylolureas, first to
soluble and then to insoluble cross- linked resins. On the alkaline side, the reaction of
urea and formaldehyde at room temperature leads to the formation of methylolureas.
When condensed, they form methylene— ether links between the urea molecules. The
alkaline products from urea and formaldehyde, and from mono- and dimethylolureas, are
as follows (Formula 1):

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—мн-снгон н-сн ан Каан

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UF Resins On the acid side, the products precipitated from aqueous solutions of urea and
formaldehyde, or from methylolureas, are low-molecular-weight m reas 'These contain
methylol end groups in some cases, through which it is possible to continue the reaction
to harden the resin. 'The monomethylolureas formed copolymerize by acid catalysis and
produce polymers and then highly branched and cured networks

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 Н-сз-нн н:-км-05-Чн нг-ны•оэ-нх-з н НМ-ОЗ-АМ- АЕ-он

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' For technical purposes it is often convenient to both arrest the reaction prior to gelation
by changing to a slightly alkaline pH and to remove some if not all of the water. The first
hardening reaction may then be came out when desired by changing once again to an acid
pH. With the present state of knowledge it appears that in the first part of the second-
stage methylol ureas condense with each other by reaction of an CH20H group of one
molecule with an NH2 group of another

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1— mix tank 2 — condensate tank 3 — screen filters 4 — reactor 5— shell and tube
cooler 6 — glycol weight measurer 7 — screen filters 8 — stabilizer Ref: Glycol 6 7 UF
Resins 3 Steam Steam 1 4 Formalin Caustic Soda Urea 5 Ammonia Water 181 Water
Urea-Formaldehyde Resin https://petrochemicalprocesses.weebly.com/p roduction-of-
urea-formaldehyde.html

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RESIN PROCESS BLOCK DIAGRAM WATER AF 37 "REACTION KETTLE

BLENDER AGING TANK RESIN PRODUCT POWDER PRODUCT ADDITIONAL
CHEMICALS -MELAMINE STE ANI /COOLISGWATER CHILLED WATER RK.OI
- 7-01 nunn 11 PRODUCT STORAGE DAY TANK SPRAY DRYER SYSTEM

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LIQUID UF / MF WAYCR coy REACTANT PRESSUR t VACUUM RECORDER

RESiN STEAM 'N RESINS PLANT Temperature : 60 •C to 70 •C to VACLA.na
WATER OUT JACKET

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Synthesis As raw materials, industrial grade 45% formaldehyde aqueous solution and
urea were used. All syntheses for this study were carried out in a stirred reactor. For
obtaining the hydroxymethylated product with the F/U initial ratio of 2.1/1, the pH of the
F solution was adjusted to 8.2—8.3 with 20% NaOH solution, and the temperature was
raised to 400C. The urea was added in small portions during 15 min, bringing the
temperature to 800C. The hydroxymethylation was ended by heating during 30 min at
80±10C. The hydroxymethylated urea was analysed and used for subsequent
polycondensation. For that, the pH was adjusted to 4.5 with formic acid and the acid
promoted reaction was accomplished at 90±10C. The time (about 100 min) was adjusted
by controlling the increase in viscosity during polycondensation to terminate the reaction
at an optimum viscosity level. Three polycondensation products prepared in the same
conditions were analysed. For obtaining the resin, the pH was adjusted to 8.5 at rapid
cooling to 60—700C, and another portion of U, equal to the first one, was added (F/U =
1.05). Heat treatment at different temperatures (60—800C) for 1.5 h (at 800C for 1 h) for
hydroxymethyl migration to U added second was carried out. After that, the dry solids
content of the resins was set to 68.5—69.5% by vacuum drying the resins at a
temperature not exceeding 400C. Analysis of resins heat treated at 65—750C was also
carried out after storage during one month.