Organic Acrylate Binder Synthesis Throug

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The key takeaways are that emulsion polymerization can be used to synthesize poly-acrylate binders for pigment printing. Different monomers like methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid and 2-hydroxyethyl methacrylate can be used for emulsion polymerization. Using different monomers allows controlling properties like mechanical strength and crosslinking. Factors like monomer composition, stirring speed during pre-emulsion and double dosing of monomers affect the mechanical properties of the synthesized poly-acrylate binder.

The different monomers used for emulsion polymerization include methyl acrylate (MA), ethyl acrylate (EA), butyl acrylate (BA), Acrylic Acid, and 2-Hydroxyethyl methacrylate.

Using different monomers allows controlling properties of the synthesized poly-acrylate binder like mechanical strength, crosslinking, elasticity, stiffness and chemical resistance.

International Journal of Scientific & Engineering Research, Volume 7, Issue 9, September-2016 1264

ISSN 2229-5518

Organic Acrylate Binder Synthesis


through Emulsion Polymerization to
ensure the best Mechanical Properties
on Applicable Substrates
Muhammad Abu Taher 1,*, K. M. Faridul Hasan2, Shamim Al Azad1, Mst. Zakia Sultana1, Md. Abdul
Mueeid2, Muhammad Ashfaq Jahangir1

1
School of Textile Chemistry & Chemical Engineering, Wuhan Textile University, Wuhan, China
2
School of Textile Science & Engineering, Wuhan Textile University, Wuhan, China

Abstract: Emulsions used as pigment binders in formulations have to cope with the challenge to assure an
outstanding film configuration and exterior as well as good mechanical properties. One strategy to fulfil this
contradictory requirement is the employment of pure poly (acrylate) resins synthesized by emulsion
polymerization. For the production of Poly-Acrylate Binder, homo and copolymers were synthesized by
emulsion polymerization using methyl acrylate (MA), ethyl acrylate (EA), butyl acrylate (BA) Acrylic Acid,
and 2-Hydroxyethyl methacrylate monomers. In accordance with recipe calculation and preparation method
our sample shows pretty good tensile and tear strengths, good abrasion resistance and stiffness, excellent

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chemical resistance and water repellence as well as air permeability.

Keywords: Emulsion, Acrylic Binder, Polymer, Crosslinking Agent, pigment.

1. Introduction

The binder film in pigment print is a three-dimensional structure, the third dimension is rather less important than the
other two[1]. The binder is a film-forming substance made up of long chain macromolecules, which when applied to
the textile together with the pigment, produces a three-dimensionally network[2, 3]. The links are formed during some
suitable fixing process, which usually consists of dry heat and change in pH value, bringing about either self-
crosslinking or reaction with other suitable crosslinking agents [4].
Binders are the mechanism used to keep the color on the fabric when using pigments for printing textiles. The choice
of binders will always depend upon the final fastness requirements as well as the cost requirements of the process[5].
Choosing a binder for pigment coloration is a complex but critical step in developing a recipe which will meet very
specific requirements[6, 7].Polyacrylate is a chemical class of acrylate polymers derived from the polymerization of
acrylic acid esters and salts. Each acrylate monomer contains a vinyl group: a pair of double-bonded carbon atoms
attached to the carbon of a carboxyl group[8]. Due to the high reactivity of carbon double bonds, acrylates polymerize
readily and are used in a variety of plastics, adhesives and chemical binder applications[9].
Pigment printing process is simple, energy saving, bright color, wide range of applications and environmental
pollution, etc., have been widely used in printing and dyeing enterprises[10]. Polyacrylate binder for pigment printing
most of the polymer emulsion with The emulsion adhesive in the textile printing can be divided according to their
chemical structure polyacrylate, butadiene, vinyl acetate, and polyurethane, wherein the polyacrylate pressure-
sensitive adhesive applications most commonly preparation conditions have a significant impact on the application
performance of the adhesive, the Investigator to be a large number of trials, but is rare[11]. emulsified by most of the
literature using a one-step emulsification, and theoretically, stars step the emulsion can be coated on the surface of the
latex particles of sufficient emulsifier to reduce the interfacial energy between the latex particles and water, and
enhance the stability of the emulsion[12]. Accordingly, in order to understand the preparation conditions on the
performance of polyacrylate pressure-sensitive adhesive applications, the emulsion polymerization to prepare the
Polyacrylate binder for pigment printing, and discuss the preparation of polyacrylate adhesive process conditions[13,
14].

1
Corresponding Author:
Muhammad Abu Taher ([email protected])

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In pigment printing of textile fabrics, pigments with little or no chemical affinity for the fibers are bound physically to
the fabric by a polymeric, film-forming adhesive[15, 16]. Both mechanical properties of the binder and adhesion to
pigment and fabric contribute to crock fastness, good mechanical properties being advantageous in resisting
deformation of the coating on rubbing[17, 18].
2. Experimental
2.1. Materials
Hard monomers (HM): Hard monomers, characterized by high Tg values, include styrene, methyl methacrylate,
ethyl acrylate and methyl acrylate. Styrene (S.T), Methyl Meth Acrylate (MMA) Supplied by Xiangcang Hongrun Co.
Ltd.China. MMA Supplier: Hubei Ocean Biotech Co. Ltd China.

Soft Monomers (SM): Soft monomers, characterized by low Tg values, include n-butyl acrylate, 2-ethyl hexyl
acrylate and iso-octyl acrylate. These monomers are longer chain alkyl acrylates and exhibit low water solubility (i.e.,
high hydrophobicity) Ethyl Acrylate (EA), Ethyl Acrylate (EA) Supplied: Changshu Jinfeng Chemical Co. Ltd China.
Butyl Acrylate (BA) supplied Butyl Acrylate (EA): Hubei Ocean Biotech Co.Ltd China.

Functional/Cross-linking Monomers (FM/CM): Functional monomer with various functional groups, such as
carboxyl or hydroxyl. Examples of functional monomers are acrylic acid and hydroxyethyl acrylate,which are very
water-soluble[19].Acrylic Acid, Acrylic Acid Supplied by : Zhengzhou Sino Chemical Co. Ltd China.
2-Hydroxyethyl methacrylate 2-Hydroxyethyl methacrylate Suppliers: Haihang industry (Jinan) Co.Ltd. China.

Emulsifier: Sodium Dodecyl sulfate (SDS) Emulsifier supplied by Zhengzhou Fuhong Biotech Co. Ltd.
China.Initiator: Ammonium persulfate (APS). Deionized Water was used to emulsify the monomers. Ammonia is
used to ensure the pH of water between7-8.

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2.2. Methods
All monomers are emulsified using emulsifiers (op10, k12)20% Req. quantity H2O +Surfactant.(stir it thoroughly for
complete dissolution of emulsifiers). Transfer this into a three neck round bottom flask and Monomers First Soft (5
min) then hard. Dissolve upto 0.5% of oxidative or reducing agent in 20 ml of water. Add remaining 80% of
calculated water. Raise the temperature 75°c and 1/3rd of APS solution (Initiator) & maintain this temperature for
another 20-30mins. Observation color of solution turns to light blue. Remaining 3/6th part of emulsion from step1 and
2/3rd of APS solution (Initiator) from step2 added and temperature in range of 80-85°c to starring 90mins. Observation
while adding emulsion and initiator light blue color of emulsion disappears. Maintain the bath temperature to 85°c and
keep stirring for another 30mins. This step monomers are converted into emulsion polymer after 30mins. Observation
After complete the process we found emulsion smells like sweet taste, it indicates completion of reaction. Then cool
down the bath temperature below 40°c. Neutralize with ammonia water (20%) because due to acrylate the PH will be
3-4 so to make it’s PH 7 add ammonia. Then filter the emulsion and dry the residue left at 105°c for 1h and then
weighs it.

3. Result and discussion


3.1. Gel Rate
After completion of the reaction, all gels, rinse, and baked in an oven at 120° C for 2 h, cooled to room
temperature in a desiccator, weighed.

X% = ×100%

Wherein: X - The gel fraction;


M - Weight of the gel;
G - Monomer weight.

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Fig. 1. Gel Ratio (%) of Prepared Binder Sample

5 samples were tested for this research where different results were found which may be due to the variation of
chemical concentration as per specified chemicals in recipe.it is seen in the figure-1 that Gel Ratio is maximum for

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sample 5 which may be due to the more concentration of Acrylate binder. Gel ratio is minimum for sample 1 where
Acrylate binder is used for 1 gram per liter. The similar effect is seen for other samples too. It could be noted that less
the gel ratio better the product (binder) & higher the gel ratio poorer the product quality.

3.2. Solid Content

Take approximately 5.5 gram of the sample and weigh it accurately in a glass dish. Place it in the oven for 4 hours at
110OC. After cooling in the decicator, weigh the dish accurately.

Solid Content (%)= 100%

G 1 = Initial weight of sample.


G 0 = Oven dry weight of the sample.

More Solid content percentage ensures that the product quality is good. Practically the % is found for 70% but 80 % is
considered as good binder. Normal treatment is performed at 60-800c for 6-7 hours. Finally the solid content is found
after the treatment of the polymer suspension at 1400C for 5 minute.

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Fig. 2. Solid content (%) of Prepared Binder Sample

3.3. Monomer conversion rate


Draw l to 2 g emulsion to clean the weighing bottle, add 1 to 2 drops of a solution of hydroquinone, and baked in

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an oven at 120°c for 2h, cooled to room temperature in a desiccator.
C% = [W (W 2 -W 1 ) / G 1 -Y] / G × 100 %
Wherein: C- monomer conversion;
W 1 - Empty weighing bottle;
W 2 - Dried weighing bottle;
W - Weight of the material;
Y - The weight of non-volatile matter in the emulsion;
G 1 - To learn the weight of the emulsion;
G - The total weight of the monomer.

Fig. 3. Monomer Conversation Rate (%) of Prepared Binder Sample

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More the monomer conversion rate the better the polymer product quality. The average monomer conversion rate
found is more than 83% which ensures that the binder quality is good.

3.4. Surface Tension Test

quality is good
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3.5. Dilution Stability Test
Fig. 4. Surface Tension (nM/m) of Prepared Binder Sample

Lower the surface tensions better the product quality. As all most all the surface tensions are within 27% so the binder

The emulsion was diluted to a solid content of 3%, then the emulsion was poured into 30ml tubes after dilution, the
liquid column height of 20cm, is placed 72h, measuring the volume of supernatant and precipitate upper portion. No
change found in the emulsion.
Table 1. Emulsion Stability Test Result

Test Type Sample-1 Sample-2 Sample-3 Sample-4 Sample-5


Acid Stability Stable Stable Stable Stable Stable
Alkali Stable Stable Stable Stable Stable
Stability
Dilution Stable Stable Stable Stable Stable
Stability

3.6. Acid and Alkali Stability

In two test tubes were charged emulsion 5g sample tested, the two tubes were then added drop wise 1ml (1mol / L)
hydrochloric acid and 1ml (1mol / L) solution of KOH. After shaking, the PH test and observe the emulsion is stable.
Then the two tubes placed at room temperature for 24h, and then observe the stability of the emulsion. No change
found, Emulsion is resistant to both acid and alkali.

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Table 2. Emulsion Stability Test Result

Sample PH Emulsion Dimensional


PH -6 H
P -7 H
P -8 H
P -9 H
P -10 Stability Stability
Sample-1 Good Excellent Good average bad Stable Stable
Sample-2 Good Excellent Good average bad Stable Stable
Sample-3 Good Excellent Good average bad Stable Stable
Sample-4 Good Excellent Good average bad Stable Stable
Sample-5 Good Excellent Good average bad Stable Stable

A polyacrylate binder for pigment printing according to claim 1, the Tg should be between 10-25OC. If Tg greater
than 25OC; then polymer becomes hard, as a result hand feel is not good. Also if the Tg goes less than 10OC the
polymer become soft but hand fell is sticky. We have taken the hard monomers 55%; soft monomers 42%;
Functional/cross-linking Monomers 3% and by applying Flory-Fox equation we have obtained the resultant Tg about
21OC.

A polyacrylate binder for pigment printing according to claim 1, the silicone is methyl trichlorosilane and methyl
phenyl dichlorosilaneare taken 12% of the total monomers will increasethe mechanical properties, thermal oxidation,
water resistance, excellent in weathering resistance, pretty good stain resistance, good air permeability. It also increase
the cross linking between polymer chain.

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A polyacrylate binder for pigment printing according to claim 1, de-ionized water will control the conductivity of the
latex.A polyacrylate binder for pigment printing according to claim 1, ammonia water (5-7% of total deionized water)
will adjust the pH 7-8.

3.7. Resultant Properties


 These binders offer the greatest durability, color stability, and dry/wet performance.
 Strong thickening ability, good water cohesive property.
 Good Evenness of the fabric.
 Good printing effect with precise printing edge.
 Toxic free like APEO and Formaldehyde
 Heat and oil resistance.
 Excellent pigment stabilization with color constancy.
 Acrylic binders have the widest range of fabric hand properties.

4. Calculation
Pigment Printing in Feel and Color Fastness of the Balance, Environmental Issues Have Not Been Applied
Satisfactorily Resolved, And The Solution to These Problems Is the Core of Synthetic Environmentally Friendly
Printing Binder, And Will Conduct Research in The Following Aspects. Reduce Product Cost. Accelerate The
Development of Lower Temperatures Less Time Crosslinking of New Products, Especially from Non-Formaldehyde
Crosslinking Agent and Catalyst for The Development of High Performance. Researches are performed into New
Methods and New Polymeric Fixation Methods such as Emulsion Polymerization, Radiation Fixing and So On.
In this article hard monomers, soft monomers and function monomers were used to get the film having pretty good
elasticity, very soft hand fell, washable, heat resistant and obviously pretty good wet & dry resistance. Organic
silicones are added to increase the mechanical properties, air permeability, water resistant and good stain resistant.
High speed stirring during pre-emulsion process and double dosing will ensure the good conversion rate of monomers
& low solid content into the copolymer.
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