che(o) : paper : 510

dissertation
report

1
 TITLE :- REACTIVE DYES

A Dissertation Submitted
To

M. G. Science Institute
Department of Chemistry
In partial fulfillment
For the Degree of

Masters of Science
In
Organic Chemistry

Submitted by
PATEL RAJ H.
P.G.Incharge Roll No: 129
(Dr. B.B.BALDANIYA) Enrollment No:202102300067

2
CERTIFICATE

3
 DECLARATION

I, PATEL RAJ H.here by, declare that the dissertation work entitled
“ REACTIVE DYES” is being submitted to M. G. Science Institute,
Chemistry Department for the partial fulfillment of Masters of Sciences
in Chemistry and specialized in Organic Chemistry. This is to also certify
that this is my own project work carried out under the guidance of
P.G.Incharge and all Profesors of M. G. Science Institute, Chemistry
Department, Gujarat University, Ahmedabad, Gujarat.

Place:Ahmedabad
Date:14th Feb 2023
PATEL RAJ H.

Roll No: 129

Enrollment No:202102300067
Uni. Exam No. :

4
 ACKNOWLEDGEMENT

The toughest of endeavors in the world is not possible without the support of a
helping hand which guides and motivates a person to take on any challenge head
on. Inputs from such helping hands are always like very essential because more
often or not certain mistakes which go unnoticed from our eyes.
I am thankful to P.G.Incharge of M. G. Science Institute, Chemistry
Department for encouragement, guidance and support from the initial to the final
level enabled me to develop an understanding of the subject.
I am heartily thankful to “R.K. SYNTHESIS LTD.” who had provided all the
required facilities to carry out the dissertation project work and nurturing my skills
to execute the requirements.
I offer my regards and blessings to all my Professors of M. G. Science
Institute, Chemistry Departmentand all the people who supported me in any
respect during the completion of the dissertation project.
Last but not the least I thank my dear parents, and friends who have been
source of support, strength, inspiration and encouragement for whatever I am
today.

PATEL RAJ H.

5
 INDEX

Sr. No. Topic

1 Introduction of Dyes

2 Classification of Dyes and their examples

3 General Application

4 Reporting of Product

5 Result & Discussion

6 Conclusion & Reference

6
 INTRODUCTION OF DYES AND INTERMEDIATES

 Dyestuff is a general industry term covering both dyes and

pigments in terms of chemistry, reactions and properties. Dyes
are intensely coloured organic compounds or mixtures used for
imparting colour to the substrates ranging from cloth, paper,
leather to plastics in a permanent fashion. There are about 600
types of dyestuffs produced in the country. A dye is generally
applied in an aqueous solution, and may require a mordant to
improve the fastness of the dye on the fibre. The basic importance
of dye lies in its product and resistant to washing. Pigments, on
the other hand, are insoluble and are important inputs to products
such as paints.

A dye intermediate is the main raw material used for the

manufacturing dyestuff. The manufacturing chain of dyes can be
traced back to petroleum based products. Naphtha and natural gas
are used for the production of benzene and toluene, which are
subsequently used for manufacturing nitro-aromatics. The nitro-
aromatics are then used for manufacturing the compounds called
dye intermediates. Hence, the third stage of production i.e., from
nitro aromatics to a dye intermediate is a part of the dyes and dye
intermediate sector. Examples of major dye intermediates are
Vinyl Sulfone.

7
 DYES

 Dyes are colored organic compounds that are used to impart color
to various substrate, including paper, leather, fur, hair, drugs,
cosmetics, waxes, greases, plastics, and textile materials.

 A dyes is a colored compound, normally used in solution, which

is capable of being fixed to a fabric. To be of use, dyes must
possess the following four properties:
 Colour
 Solubility in water
 Ability to be absorbed and retained by fiber
(substantivity) Ability to withstand washing, dry
cleaning and exposure to light.

 The dyes has colour due to the presence of chromophore and its
fixed property to the acid or basic groups such as OH, SO3H,
NH2, NR2, etc.

 The polar auxochrome makes the dye water-soluble and binds the
fabric by interaction with the oppositely charged groups of fabric
structure

8
Classification of Dyes

9
 CLASSIFICATION OF DYES

 There are several ways for classification of dyes.

 Classification based on the source of materials
 Classification of the dye- Based on the nature of
their respective chromophores.
 Classification by methods of application.

 CLASSIFICATION BASED ON THE SOURCE OF

MATERIALS

 A very common classification of the dyestuff is based on

the source from which it is made. Accordingly, the
classification could be:
• Natural Dyes
• Synthetic Dyes

NATURAL DYE

 Natural dyes are dyes or colorants derived from plants,

invertebrates, or minerals.
 The majority of natural dyes are vegetable dyes from plant
sources. E.g., roots, berries, bark, leaves and wood.
 organic sources include fungi and lichens.

10
 Two natural Dyes
1 Alizarin :-
 Alizarin is a red dye astracted from the roots of the
madder plant, rubiatinctorium.
 Two other red dyes were obtained from scale insect. This
include kermes obtained from coccus ilicis which infects the
kermes oak, and Cochineal obtained from coccus, which lives
on prickly pear cactus in Mexico. Cochineal dye can be
obtained from an estimated 200000 insects.

2 Indigo :-
 Probably the oldest known dye is the blue dye indigo,
obtained in Europe from the leaves of the dyers woadherb,
indigo plant indigo few huratinctorial.
 Even by Mordant standard both alizarin and indigo have very
good dyeing properties, and indigo remains a favorable dye for
denim, although synthetic indigo has replaced the natural
materials

11
 Classification of Natural Dyes :-

 Mainly two types of natural Dye classification are done

based on Chemical class and on colour.

 Based on Chemical Classes:-

 The natural organic dyes and pigments cover a wide

range of Chemical Classes. Ex. Polymethines.
 Ketones, Imines, Quinines, Anthraquinonoid,
Naphthoquinones, Flavones, indigoids And chlorophyll.

 Based on Colour :-

 In the colour index, the dye are classified according to

chemical constitution as well as major Application classes.
Within application class, the dyes are arranged according to
hue. Natural dyes form a separate section. The no. Of dyes
in each hue are given below. Some dyes produce more than
one colour.
 Application of Natural Dyes :-
 Natural dyes are known for their use in colouring of food
substrate, leather as well as naturalfibres like wool, silk and
cotton as major areas of application since pre- historic
times.
 Plant leaves, fruits and other are potential sources of natural
dyes because of their easy availability and abundant nature.
India has a very rich tradition of using natural dyes. The art
and craft of producing natural dyed textile has been practiced
since ages on many villages by traditional expert crafts-
persons in the country.

12
 SYNTHETIC DYES
 Almost all the colors that you see today are synthetic dyes
.Synthetic dyes are used everywhere in everything from clothes
to paper , from food to wood. This is because they are cheaper
to produce, brighter, more colour fast, and easy to apply to
fabric.
E.g. Acid dye, Azo dye, Basic dye, Mordant dye, etc.

 CLASSIFICATION OF DYES & THEIR EXAMPLES

1. Acid Dyes :
 Acid Dyes are water Soluble anionic dyes that are Applied to
fibers such as Silk, wool, nylon and modified acrylic fibers using
neutral to acid dye baths.
 Acid Dyes are not Substantive to cellulosic fibers. Most
synthetic food colors fall in this category. Examples of acid dye
are Sulfonic acid, Malonic acid.
Ex. Sulfonic acid:- ( RSO3H )
Malonic acid :- ( COOH-CH2-COOH )

MALONIC ACID

13
2. Basic Dyes :
 Basic Dyes are Water Soluble Cationic dyes that are mainly
applied to acrylic fibers, but find some use for wool and Silk.
Usually acetic acid is added to the dye bath to help the uptake of
the dye onto the fibre.
 Basic Dyes are also used in the coloration
of paper.
Ex. Methylene blue, Safranin.

SAFRANIN
3. Direct Dyes :
 Direct dyes are used on cotton, paper, leather, wool, silk and
nylon. They are also used as PH indicators and as biological
stains.
Ex. Congo red & Direct red

14
4. Mordant Dyes :
 Mordant Dyes are require a Mordant, Which improves the
fastness of the dye against Water, Light and perspiration.
 The Most important Mordant Dyes are the Synthetic Mordant
Dyes, or Chrome dyes, used for Wool.
Ex. Urine dye

5. Reactive Dyes :
 A Reactive dye is a colouring Compound Which has a suitable
group, capable of reforming a Covalent bond between Carbon
atoms.
Ex. YELLOW FG

15
6. Disperse Dyes :
 Disperse Dyes were originally developed for the dyeing of
Cellulose acetate, and are Water insoluble.
 Their main use is to dye polyester, but they can also be used to
dye, nylon, Cellulose triacetate, and acrylic fibers.
Ex. 4-amino Azobenzene

7 Sulfur Dyes :
 Sulfur Dyes are inexpensive dyes used to dye cotton with dark
colors. Dyeing is effected by heating the fabric in a Solution of
an Organic Compound, typically a nitro phenol derivative, and
Sulfide or Polysulfide.
Ex. Indophenol , Sulfur black

SULFUR BLACK

16
8 Chromophoric Dyes :
 Dye molecules contain to group the Chromophore and the
auxochrome. The Chromophore is a group of atoms which control
the colour of the dye. Chromophoric Dyes are used in food
colouring, fabric dyes, PH indicators.
Ex. Chlorophyll, beta carotene.

9 Azoic Dyes :-
 Azoic dyeing is a technique in which an insoluble Azo dye is
produced directly onto or within the fibre.
 Azo dyes are used in dyeing textile fibres, particularly cotton but
also Silk, wool, viscose and Synthetic fibres.
Ex :- Fluorescein dye and Polypropylene fibers.

17
 General Application of Dyes

 Dye, Substance used to impart color to textile, paper, leather,

and other materials. Such that the coloring is not readily altered
by washing,heat,light or other factor to which the material is
lightly to exposed. Dyes differ from pigments, which are finely
ground Solids dispersed in a liquid, such as a paint or ink or
blanded with other materials.
 Reason for the colour of a dye :-
 Many theories have been given to correlate the colour of dyes
with their molecular structure. In 1876, Otto Witt, a German
Chemist observed that the colour of a dye is due the certain
groups containing multiple bonds known as chromophores.
Some examples of the chromophores are nitro group(-NO2),
nitroso group(-NO), carbonyl group(-CO-), ethylenic bond(-
C=C), acetylenic bond etc. As the number of chromophores
increases for a dye, the colour of the dye also deepens [17–21].
He also observed that not only the chromophores are
responsible for the deepening of colour but also there are
certain groups which itself does not act as the chromophore but
the presence of which deepens the colour of the dye. These
groups are known as Auxochromes. Some examples of the
auxochromes are -OH, --NH2, -NHR, -NR2, X (Cl, Br or I),
COOH. 1,3- Dinitronapthalene (Figure 1) is pale yellow but
the dye Martius Yellow (2,4- Dinitro-1-naphthol) is orange-red
(Figure 2) [17–21]. Here group -OH is acting as the
auxochrome as the presence of it has deepened the colour of
1,3- Dinitronapthalene.
 To explain the origin of colour, Valence Bond Theory (VBT)
and Molecular Orbital Theory (MOT) are proposed in modern
time. The vital difference between the VBT and MOT is that
in VBT electrons are treated in pairs while in MOT electrons
are treated singly [17–22].

18
 History of Reactive Dyes
 On the occasion of 100 year’s celebration of synthetic dyes
manufacturing, two chemists of ICI company (UK) named
Stephen and Ratted tried to manufacture a new dyestuff. Thus
they succeed to invent a new dye in 1965, which was named
REACTIVE DYE. This was manufacture for dyeing cellulosic
fabrics. The first three reactive dyes were PROCION
YELLOWR, PROCION BRILLIANT RED 2B and
PROCION BLUE 3G for this effort they were awarded gold
medal of the society of dyes and colorists for the year 1960.
 Reactive dyes
 dyes form a new chemical compound when they come into
contact with a fiber molecule.
 Reactive dyes are applied either from a solution with high pH
or from neutral solutions that are later alkalized through a
separate process.
 different shades are brought out by applying heat to the dyed
textile. Originally, reactive dyes were applied to cellulosic
fibers but today other fibers are also dyed using reactive dyes.
 dyes form a covalent bond between fibre and dye. They are
classified depending on the reactive group present and the
optimized conditions in which they are best used.
 About 95% of reactive dyes are azo dyes covering an entire
range of colors. Blues and greens are also provided by
anthraquinone and phthalocyanine structures.

19
 Properties of Reactive Dyes
 All types of Shades are available from these dyes.
 Reactive Dyes are found in powder, liquid, and print paste form.
 Reactive Dyes are soluble in water.
 They have very good light fastness with a rating of 6. The dyes have
very stable electron arrangements and can protect the degrading
effect of ultra- violet rays. Reactive dyes have good perspiration
fastness with rating 4-5.
 Textile materials dyed with reactive dyes have very good wash fastness
with a rating of 4-5 dye to strong covalent bonds formed between
fibre polymer and reactive group of dye.
 Reactive dye gives brighter shades and has moderate rubbing fastness

Factors to Be Considered During Reactive Dyeing

 PH – Strong alkaline PH is required ranging from 10.5-11.2
 Temperature – Dyeing temperature depends on the brand of dye used.
 Concentration of electrolyte – The depth of Shade is the determining
factor of electrolyte concentration.
 Time- Ranges from 60-90 minutes.
 Liquor ratio – Higher liquor ratio gives bet ter efficiency.
Advantages of Reactive Dyeing
 Brilliant, bright colours.
 Permanency of the colour
 Covalent fixation – high wash fastness ( WF )
 Various temperatures, including low energy ( Cold Dyeing )
Disadvantages of Reactive Dyeing
 Incomplete fixation ( Problem with hydrolysis )
 Need for wash – off ( for High WF )
 Need for high Concentration of salt

20
 Precautions for Reactive Dyeing

 Hot water should not be used for high reactive dyes because
there will be a possibility of hydrolysis.
 Prepared dye solution can not be stored for later use also because of
dye hydrolysis.
 For making print paste, low reactive dyes are used.
 It is dangerous if there is the inhalation of the dust of reactive
dyes, So a protective mask is required.
 A limited storage period is applicable to most of the reactive dye.

Reporting Of Yellow FG

 Contents

 Introduction
 Experiment – 1
Synthesis of YELLOW FG
 Experiment – 2
Synthesis of YELLOW FG Derivative

 Conclusion
 Reference

21
22
Classification of Dyes

23
 INTRODUCTIONS

 A dye is a coloured substance that has an affinity to the substrate to

which it is being applied. The dye is generally applied in an
aqueous solution.
 Reactive dyes are most popular and versatile nature of organic dyes,
which are mostly applied in textile processors. This dye react with
cellulose to create a Covalent bond between Cellulose and dye
molecule.

 Preparation of dye :-
 Reactive Yellow FG
 Material:
 Para Base Vinyl Sulfone (VS)
 Conc. HCL
 NaNO2
 SPCP (Sodium Pentachloro phenate)
 Caustic lye
 Sodium Bicarbonate
 Water
 Ice

24
 Pocedure
 In one container take 200 ml water then add 32 gm real PARA
BASE VS (purity 96%) and 25 ml conc. HCL stire it & cool it
below 5C with ice.
 Dissolve 8 gm NaNO2 in some water and add this clear solution
into above solution keeping temperature below 5C
(Diazotization). The mixture allowed to stirr 1 hour. At this
point check +ve SI & CR.
 Check presence of Nitrite by Starch Iodide paper. If Black spot
seen on SI paper SI is Positive and If Black spot not seen SI is
Negative.
 Also check presence of HCL by Congo Red paper which shows
Blue spot which confirms the presence of HCL.
 If SI remain positive then add Sulfamic Acid to Negative SI
paper. Once the SI paper shows Negative then charge coupler.

25
PART:-1 (Yellow FG)

• Take 17.5 gm SPCP (Sodium Pentachlorophenate) (Coupler)

in 200 ml water. Dissolve in 6.5 ml Caustic lye at pH 8.5-9.
• Add this clear solution into above Diazo Solution. Stire 1 hour
& Cool below 10C.
• Raise pH 4.5 with 8 gm Sodium Bicarbonate. Stire for 1 hour.
• Check TLC against STD.
• Isolate it with salt/ KCl. Check spot.
• Filter & Dry it.

REACTIVE YELLOW FG

26
  Calculation of yield :-

Theoretical Yield :- molecular weight of product × weight of s.m.

molecular weight of s.m.

= 578 × 17.5
281

= 35.9 gm

 Practical yield :- weight of product obtained

= 31.8 gm

 % of yield :- practical yield × 100

Theoretical yield

= 31.8 × 100
35.9

= 88.57%

27
 Result & Discussion

1 . Theoretical yield = 35.9 gm

2. Practical yield = 31.8 gm

3. % of yield = 88.57 %

4. M.p of product = 156 C

28
29
Discussion
 Here from Strength Calculation Report based on UV
spectroscopy:
 Da* value is negative (-) therefore it Shows Shade is
greener.
 Db* value is negative(-) therefore it shows Shade is less
Yellower
 DC* value is also negative (-) therefore it shows Shade is
Duller.
 DE* is a difference of Sample against standard
dye. Here strength is average than standard
 UV strength of sample is:
105.536%

 Solvent System

30
 IR-DATA OF REACTIVE YELLOW FG

FUNCTIONAL GROUP IR DATA

 Aromatic (C=C ) 1600 cm-1

 Alkane ( -CH ) 3100-3000 cm-1

 Aromatic (-CH ) 1200-1650 cm-1

 Sulfonic acid ( S-O ) 1350-1342 cm-1

 Primary Amine ( R-NH ) 3500 cm-1

 (R- C – N ) 1180-1360 cm-1

 ( CH – COOH ) 1725-1700 cm-1

31
 Reactive ORANGE 2R (Derivative)

 Material:-

• Para Base Vinyl Sulfone (VS)

• Conc. HCL
• NaNO2
• Sodium Napthionate
• Sodium Bicarbonate
• Water
• Ice

 Chemical Reaction

ORANGE 2R(DERIVATIVE)

32
PART:-2 (Orange 2R) (Derivative)

• Take 16 gm Sodium Napthionate (Coupler) in 200 ml

water.
• Add this clear solution into above Diazo Solution. Stire 1 hour
& Cool below 10C.
• Raise pH 4.5 with 14 gm Sodium Bicarbonate. Stire for 1
hour.
• Check TLC against STD.
• Isolate it with salt/ KCl. Check spot.
• Filter & Dry it.

 Calculation of yield :-

 Theoretical yield :- molecular weight of product × weight of s.m

molecular weight of s.m
= 537 × 16
281
= 30.57 gm

 Practical yield :- weight of product obtained

= 24.5 gm

 % of yield :- practical yield × 100

Theoretical yield
= 24.5 × 100
30.57
= 80.14 %

33
 Result & Discussion

1. Theoretical yield = 30.57 gm

2. Practical yield = 24.5 gm

3. % of yield = 80.14 %

4. M.P of product = 124 C

34
35
Discussion
 Here from Strength Calculation Report based on UV
spectroscopy:
 Da* value is negative (+) therefore it Shows Shade is
less green.
 Db* value is negative(+) therefore it shows Shade is
Yellower.
 DC* value is also negative (+) therefore it shows Shade
is Brighter.
 DE* is a difference of Sample against standard
dye. Here strength is average than standard
 UV strength of sample is:
38.532%

Solvent System

36
 IR DATA OF ORANGE 2R (DERIVATIVE)

FUNCTIONAL GROUP IR DATA

 Aromatic (C=C ) 1600 cm-1

 Alkane (-CH ) 3100-3000 cm-1

 Aromatic( -CH ) 1200-1650 cm-1

 Sulfonic acid ( S-O ) 1350-1342 cm-1

 Primary Amine (R-NH2) 3450-3350 cm-1

 (R- C – N ) 1180-1360 cm-1

37
 Observation Of Dye On Cotton

Std.Yellow FG Yellow FG Orange 2R(Derivative)

38
 CONCLUSION

 Reactive dyeing is truly an important dyeing phenomenon for

cellulose materials.
 Among different classes of dyes for cellulosic fibres the reactive
dyes are the only one that can attach themselves to the fibres by the
co-valent bond.
 Reactive dyes are coloured compound which contain one or two
groups capable of forming co-valent bond between a carben atom or
phosphorous atom of the dye ion or molecule and an oxygen or
sulphar atom of a hydroxyl, an amino or a mercapto group (-SH)
respectively.
 The purpose of the present investigation is to obtain reactive dyes
with a higher degree of reactivity.

39