FORMULATION OF TUNABLE CYANOACRYLATE-BASED ADHESIVE

BY

ISAAC ONYANGO ODHIAMBO

(BSc. Industrial Chemistry (Degree), Mount Kenya University)

A DISSERTATION RESEARCH PROPOSAL SUBMITTED TO THE DEPARTMENT

OF NATURAL SCIENCE IN THE SCHOOL OF PURE AND APPLIED SCIENCE IN
PARTIAL FULFILMENT OF THE REQUIREMENT FOR THE DEGREE IN
BACHELOR OF SCIENCE IN INDUSTRIAL CHEMISTRY

SCHOOL OF PURE AND APPLIED SCIENCE DEPARTMENT OF NATURAL

SCIENCE

MOUNT KENYA UNIVERSITY

2024

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 DECLARATION

This project is my original work and has not been presented for a degree in any other university

Name of student: Isaac Onyango Odhiambo

College: Mount Kenya University

Faculty/school/institute: Pure and Applied science

Department: Natural Science

Course: BSIC. Industrial Chemistry

Title of the work: formulation of tunable cyanoacrylate-based adhesive

I declare that this proposal is my original work and has not been submitted anywhere for an
award of degree where other people’s work.

Student Name Isaac Onyango Odhiambo

Signature………………………Date………………………………..

I understand what plagiarism is and am aware of the university policy in this regard.
This proposal has been submitted for examination with my approval as university supervisor

Lecture’s name

Dr. Dennis Gitau…………………………………………………………

Signature……………………………………… Date…………………

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 ABSTRACT

Cyanoacrylate is several “cynoacrylic esters that cure to form a strong adhesive bond. They are
usually sold as contact adhesives under trade names such as super glue and Krazy glue.” By
curing, they can form bonds instantly to a variety of surfaces including Plastics, wood, and glass,
and have been applied in the building industry to hold building stones in position. However, it
has a wide variety of applications and a positive impact it still possesses a major back clash, due
to its fast rate of curing through anionic polymerization of its components in the presence of
water or moisture (hydroxyl ion), hence it poses a threat when it spills off. In some instances, the
rate of curing is observed to be at a slower rate than the expected rate. The intended goal of this
study is to observe the effects of sodium hydrogen carbonate known by the marketed name
Baking powder on the rate of curing of cyanoacrylate adhesive and the retardation effect of citric
acid on the curing of cyanoacrylate. This study will help by notifying the way of maximization
of curing of cyanoacrylate and retardation of the curing of the adhesive to help control accidental
spills .By use of an electric weighing balance, wood planks, Stopwatch, weighing masses of 20-
100g, String, and 25g of methyl cyanoacrylate.

Keywords: Curing, anionic polymerization, sodium hydrogen carbonate, citric acid, hydroxyl
ion

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 Table of Contents
ABSTRACT....................................................................................................................................3
CHAPTER 1: INTRODUCTION................................................................................................5
1.1 Background Information........................................................................................................5
1.2 Statement of the Problem.......................................................................................................7
1.3 Objectives...............................................................................................................................7
1.3.1 General Objective............................................................................................................7
1.3.2 Specific Objectives..........................................................................................................7
1.4 Justification of The studies....................................................................................................8
1.5 Scope of The study.................................................................................................................8
CHAPTER TWO: LITERATURE REVIEW.............................................................................9
2.1 Introduction............................................................................................................................9
2.2 Theoretical Review................................................................................................................9
2.3 Synthesis and processing.....................................................................................................10
2.4 Condensation-DE polymerization Reaction to Produce Alkyl 2-Cyanoacrylate.................13
2.5 Acceleration of anionic polymerization of Cyanoacrylate-based adhesives By Sodium
hydrogen Carbonate (Baking powder).......................................................................................14
2.6 Retardation effect of Citric acid on anionic polymerization of cyanoacrylate-based
adhesives....................................................................................................................................14
CHAPTER THREE: RESEARCH METHODOLOGY..........................................................16
3.1 Research Design...................................................................................................................16
3.2 Sample size and Sampling Technique.................................................................................16
3.3 Research Instruments...........................................................................................................16
3.3.1 Apparatus.......................................................................................................................16
3.3.2 Reagents........................................................................................................................17
3.4 Data collection Procedure....................................................................................................17
3.5 Data Processing and Analysis..............................................................................................18
3.6 Research Plan.......................................................................................................................18
3.7 Research Budget..................................................................................................................18
REFERENCES............................................................................................................................19

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 CHAPTER 1: INTRODUCTION
1.1 Background Information
The synthesis of cyanoacrylate adhesives was initially accomplished in the year 1949.
These adhesives possess a typical chemical formula signified as CH2=C (CN) CO2R, where R
signifies an organic moiety, such as methyl (CH3) (Pismenskaya et al., 2019). Due to the
markedly polar characteristics of the nitrile (CN) and esters (RCOOR) functional groups, these
compounds exhibit rapid reactivity towards any alkaline surface, particularly in the presence of
moisture. The inherent chemical structure of cyanoacrylate adhesives makes them prone to swift
reactions, especially when exposed to basic environments, and this is largely attributed to the
highly reactive nature of the nitrile and ester groups. The molecules readily polymerize to form

. They are commonly, intact, curable at room temperature, and have low
viscosity. These properties play a huge part in the rapid curing ability and formation of strong
thermoplastic with excellent adhesion with the surface or substrate they come in contact with,
also makes cyanoacrylate the most widely used adhesive in both industrial, pharmaceutical, and
structural applications (Pismenskaya et al., 2019). Numerous investigation and research has been
carried out on the self-healing cementations material by many researchers (Li et al., 1998; Joseph
et al., 2011; Sun et al., 211). During the investigations, the adhesive was stored inside a hollow
glass tubular capsule, the agent was released when a crack in the cementations matrix crossed
and broke the brittle glass.
Pismenskaya et al. (2019) research laid the foundation for our understanding of
cyanoacrylate, an acrylic resin famed for its rapid bonding skills. As consistent with individuals
on HowStuffWorks.Com, cyanoacrylate bureaucracy robust bonds nearly instantly. The
molecules within the acrylic resin go through a reaction upon touch with hydroxyl ions found in
water, a method facilitated by using the trace quantities of moisture within the air and on
maximum substrate surfaces. This adhesive can hastily and securely adhere to numerous items,
carrying out a chemical phenomenon known as anionic polymerization. This system now not
commonly used removes water, contributing to bond formation, however also generates
warmness. Interestingly, the realistic application of cyanoacrylate in medical contexts strains
returned to the Vietnam War, where it turned into hired for the closure of organ and skin injuries.

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However, its utilization turned into curtailed because of toxicity issues. Notably, one of a kind
types of cyanoacrylate, inclusive of Methyl 2-cyanoacrylate and Ethyl 2-cyanoacrylate, are to be
had under the label of Super Glue. Until recently, 1-2-Cyanoacrylate stood because the primary
commercially to be had shape. However, in 1998, the United States FDA permitted 2-octyl-
cyanoacrylate as a tissue adhesive and for skin closure due to its lower toxicity and decreased
capacity for skin reactions. This improvement marked a significant stride in increasing the
repertoire of cyanoacrylate-based totally products for clinical programs.
According to Taghreed et al. (2021), the accessibility and massive use of Cyanoacrylate-
based totally products for domestic functions are attributed to their several advantages. Despite
the potential for minimum dangerous outcomes, which may additionally variety from infection to
excessive burns requiring surgical interest, injury prevention stays the maximum critical
component. Remarkably, the pH levels of Cyanoacrylate-based totally adhesives display no
considerable observable distinction even after publicity to shampoo, emphasizing their balance.
Proper storage situations play a pivotal position in retaining the efficacy of Cyanoacrylate
adhesives. Storage in cool, dark, and dry environments is suggested, as high temperatures can
lessen viscosity and effect effectiveness. Light and moisture are diagnosed as accelerators of the
polymerization system, highlighting the want for producers to offer facts on premier storage
conditions and shelf lifestyles. Typically, Cyanoacrylates have a shelf life of 12 months, after
which polymerization, hardening, and curing can also arise at a sure charge. While unmarried-
use disposable bins are well-known for scientific-grade cyanoacrylate used in surgical operation,
some emergency departments and hospitals have mounted storage centers for used adhesives.
This lets in for the reuse of a single vial in a couple of wound-closing processes across different
patients, as mentioned in literature.
Joints shaped with the aid of popular-motive cyanoacrylate showcase high shear and
tensile houses, with brittleness being a commonplace feature. These joints can face up to
temperatures starting from -54°C to about 82°C under low humidity, with minimum adjustments
found indoors through the years. Outdoors, degradation may be minimum, contingent at the
substrate kind. While catalysts are not strictly essential for cyanoacrylate polymerization, they
could expedite curing. Phenyl ethyl-ethanolamine is a broadly used catalyst, but it has the
disadvantage of shortening joint lifestyles and now not promoting curing between big gaps. The
addition of inhibitors, along with Sulfur Dioxide, can stabilize cyanoacrylate adhesives.

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However, there are challenges associated with inhibitor addition, inclusive of issue in uniform
incorporation and capacity break out from adhesive bins by using diffusion at some point of
storage (Pismenskaya et al., 2019). For anionic polymerization inhibition, cyclic natural sulfates,
sulfites, sulfoxides, and sulfinates, like 2-oxo-1, three, 2-dioxathiolanes, had been diagnosed as
effective inhibitors. Notably, 4-5-Dimethyl-2-oxo-1, 3, 2-dioxathiolane (B.P 1850C) is
highlighted as a specific inhibitor with advantages in ease of addition, contrasting with gaseous
inhibitors.
1.2 Statement of the Problem
Cyanoacrylate-based adhesives have wide applications in industrial and structural
applications worldwide. They possess numerous advantages as compared to latex-derived
adhesives for instance, the high rate of curing as compared to other types. However the rate of
anionic polymerization of the Cyanoacrylate-based adhesives has not been maximized to the
fullest, this has created minor problems in its application as they take a long duration to cure.
The durability of the joint formed when exposed to water or a moist environment has a short life.
They however have an accelerated curing when used on cotton or wool substrate, leading to a
burn or starting fire. This has created concern on how to retard the process of polymerization, to
help manage curing occurring due to accidental spillage. Which may lead to burn or start a fire?
Medical research and studies have shown that cyanoacrylate-based adhesives cause irritation on
human skin and may also cause burns depending on the quantity. Due to high anionic
polymerization in the presence of moisture or water, Washing of the spillage with water is not
advisable. Hence there is demand for a suitable retardant.
1.3 Objectives
1.3.1 General Objective
1. The main aim of this study is to be able to retard and accelerate the anionic
polymerization of cyanoacrylate-based adhesives, by using a suitable accelerator and
retardant.
1.3.2 Specific Objectives
1. To determine the effect of Sodium hydrogen carbonate (Baking Powder) on the curing
duration and strength of the formed joint of Cyanoacrylate-based adhesives.
2. To determine the retardation effect of Citric acid on Curing
3. Time and strength of joint formed of Cyanoacrylate-based adhesives.

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 4. To relate the joint strength to Bond type formed during the anionic polymerization of
Cyanoacrylate-based monomers.

1.4 Justification of The studies

The research will be carried out to investigate anionic polymerization of Cyanoacrylate-
based adhesives with help of suitable accelerator. This study will also cab side effects associated
with the existing accelerators e.g. Acetone-based accelerators which are highly volatile, this
expose the user to headache, fatigue, nausea, irritation of nose, throat and airway. Due to high
volatility of the acetone-based accelerators; rapid evaporation causes formation of gaps within
the joint structure, causing joint brittleness and poor bond strength (Pismenskaya et al., 2019).
They are also highly flammable this discourages the use of these accelerators at high
temperature. The research study will note the advantages of Baking powder (sodium hydrogen
carbonate) as an accelerator of anionic polymerization of cyanoacrylate-based adhesives as it
creates a faster setting, compactness and curing time of the joint. The research will also cover the
retardation effect of citric acid on cyanoacrylate-based adhesives polymerization and curing
time. The study will also help notify the type of joint formed due to retarding of anionic
polymerization of the cyanoacrylate-based adhesives. The outcome of the study will help
categorize and understand the importance of baking powder and citric acid as effective
accelerators and retardants respectively.
1.5 Scope of The study
The study will analyze effect of sodium hydrogen carbonate (Baking powder) and Citric
acid on polymerization of Cyanoacrylate-based adhesives ,Based on percentage mixture content
relating to duration of curing and joint strength(Bond strength).The cyanoacrylate-based
adhesive will be sampled from Crystal Adhesives Ltd Manufacture in Nairobi county. The period
of the study will be three months and the cost of the study will be one thousand Kenyan
shillings.

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 CHAPTER TWO: LITERATURE REVIEW
2.1 Introduction
Cyanoacrylate-based totally adhesives have garnered sizable global attractiveness due to
their exquisite versatility in bonding and reinforcing materials. This magnificence of adhesives
has emerge as a favored desire, particularly inside the realm of prototyping, owing to its
remarkable adhesive homes that transcend a numerous array of materials. The adhesive
capabilities extend seamlessly throughout plastics, rubber, metals, ceramics, timber, glass, paper,
cloth, cement, and even organic tissues (Chandrasekharan et al., 2019). The huge applicability of
cyanoacrylate-based adhesives makes them vital in numerous industries, offering a reliable
answer for bonding and strengthening exclusive components. The discovery of cyanoacrylate's
adhesive homes is a conventional instance of serendipity in clinical exploration. In 1951,
researchers at Eastman Kodak Company stumbled upon the adhesive ability of cyanoacrylates
whilst undertaking refractive index measurements on ethyl 2-cyanoacrylate samples initially
designed for warmth-resistant jet aircraft canopy programs. The unintentional discovery took
place whilst the ethyl 2-cyanoacrylate pattern all at once adhered to the prisms of the
refractometer all through the experiment (Chandrasekharan et al., 2019). Despite the initial
panic, the scientists swiftly recognized the massive capacity and price of this adhesive fabric.
This serendipitous locating marked the start of the considerable use of cyanoacrylate-primarily
based adhesives, revolutionizing the field of bonding technology and imparting a dependable
solution for various bonding applications.
2.2 Theoretical Review
Cyanoacrylates are available in various forms, differing in the length and complexity of
their molecular chains. These forms include methyl, n-butyl, isoamyl, isohexyl, and octyl
cyanoacrylates (HW, 1959). In the field of periodontics, reports shows a case where
cyanoacrylate adhesive was used to affix a resorbable membrane to the recipient bone in a
vertical defect, facilitating guided tissue regeneration with aesthetically pleasing results observed

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four years post-procedure. The solubility of these adhesives was thoroughly investigated using a
range of organic solvents, such as hexane, dichloromethane, and chloroform (Winther et al.,
2015). The optimal sample preparation method was determined through meticulous
experimentation. Employing an advanced Capillary Electrophoresis method, a comprehensive
trace anion profile of cyanoacrylate adhesives was generated (Pismenskaya et al., 2019). The
results indicated that the adhesives exhibited instability within a two-year timeframe, after which
both stability and performance were carefully assessed.
In addition, the 2-cyanoacrylates, especially the n-butyl and isobutyl derivatives, have
been extensively tested and used as a medical adhesives in several surgical specialties. Their
ability to polymerize on moist surfaces and thereby glue skin and mucous membranes and
because they biodegrade make them suited for this purpose (Xie et al., 2022). “The
cyanoacrylate functions as adhesives by molecular attraction with smooth dense surface as well
as mechanical adhesion caused by grip action or interlocking of the set adhesive in the surface
irregularities, cavities, or pores of rough surface.” In addition, if a nucleophile group on a protein
initiates the polymerization reaction, a covalent bond to adhesive is formed which would add to
bonding strength in living tissues (Winther et al., 2015). The short-chain cyanoacrylates forms
bonds with a higher tensile strength with different non-biological materials compared to long-
chain homologues, for instance on aluminum surfaces the methyl and ethyl homologues form
bonds at least twice as strong as the butyl homologue. This makes them better suited for
industrial and household use than the higher homologues (Chandrasekharan et al., 2019). For a
homologue series of cyanoacrylates ranging ranging from methyl up to octyl, the time for
polymerization in water is increased from 10 seconds for the short-chain to 5 minutes for the
long-chain homologues.
2.3 Synthesis and processing
Cyanoacrylate monomers are commonly identified by their acrylate backbone, featuring
two electronegative groups, as depicted below. These groups, known for their electron-
withdrawing properties, are capable of engaging in anionic polymerization when exposed to
bases (HW, 1959). This polymerization process leads to the formation of a polymer with a glass-
like structure. The characteristic acrylate backbone, coupled with the presence of these
electronegative groups, enables the initiation of a polymer chain through anionic polymerization,
ultimately yielding a polymer with unique properties reminiscent of glass. Cyanoacrylate

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monomers, outstanding by way of their acrylate spine and two electronegative organizations,
represent a class of adhesive substances famend for their first rate bonding talents (Winther et al.,
2015). The acrylate spine serves because the structural foundation, at the same time as the
electronegative agencies, acknowledged for their electron-taking flight characteristics, play a
pivotal position in anionic polymerization while exposed to bases, as elucidated by HW in 1959.
This polymerization manner induces the development of a polymer with a different glass-like
shape, characterised through robust and sturdy residences. The inherent acrylate spine, coupled
with the electron-retreating companies, helps the initiation of a polymer chain through anionic
polymerization, resulting in a final product with particular attributes reminiscent of glass.
The superb homes of cyanoacrylate polymers stem from their unique molecular shape.
The acrylate spine, with its characteristic double bond, enables the anionic polymerization
manner while uncovered to bases. The electronegative companies attached to the spine play a
crucial function on this polymerization, improving the electron-withdrawing homes and
contributing to the general stability of the polymer chain. The resulting glass-like shape imparts
exquisite strength and resilience to the cloth, making cyanoacrylate polymers extensively applied
in diverse adhesive packages. The awesome aggregate of the acrylate spine and electronegative
corporations not only enables efficient polymerization but also consequences in a final product
with particular houses, making cyanoacrylate monomers a key player in the subject of superior
adhesive technology.
The variability in adhesive properties among a-cyanoacrylates underscores the
importance of carefully selecting the appropriate type for specific applications. Within the realm
of adhesive applications, alkyl 2-cyanoacrylates emerge as the preferred choice, as highlighted
by various studies (Pooresmaeil et al., 2022). The distinguishing factor that sets alkyl 2-
cyanoacrylates apart is the incorporation of highly effective electron-withdrawing functionalities,
namely cyano (CN) and carboxyl ester (COOR) groups. The unique combination of these
electronegative groups imparts distinctive characteristics to alkyl 2-cyanoacrylates. Specifically,
their ability to engage in rapid anionic polymerization with weak bases like water and alcohols is
notable. This chemical process culminates in the creation of a high molecular weight polymer
through the formation of a carbanion (Pooresmaeil et al., 2022). One of the key features
contributing to the exceptional performance of alkyl 2-cyanoacrylates in adhesive applications is
the remarkable stability of the carbanion. This stability is achieved through the electron-

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withdrawing nature of both the cyano (-CN) and ester (-COOR) groups. The presence of these
groups ensures a robust and enduring carbanion structure, which, in turn, underpins the rapid-
setting characteristics exhibited by these materials (Chandrasekharan et al., 2019). The quick-
setting nature of alkyl 2-cyanoacrylates is of paramount importance in adhesive scenarios where
rapid bonding and solidification are desired.
The production of alkyl a-cyanoacrylate monomers involves a condemnsation-
depolymerization method known as the Knoevenagel reaction. Initially, an alkyl a-cyanoacrylate
polymer is synthesized through the condensation reaction of alkyl cyanoacetate with
formaldehyde in the presence of a base (for instance, amine) (Pooresmaeil et al., 2022). Isolation
of the alkyl a-cyanoacrylate monomer during this process is challenging due to the initiation of
cyanoacrylate polymerization by the base catalyst. The base catalyst is typically neutralized at
the end of polymerization through the addition of small amounts of an acidic compound like
phosphoric anhydride. Subsequently, the polymer undergoes depolymerization at elevated
temperatures (140–260 °C) under acidic conditions (for example, phosphoric anhydride) to
obtain the alkyl 2-cyanoacrylate monomer. To ensure stability during manufacturing, storage,
and transport, alkyl a-cyanoacrylate monomers must be well-stabilized to prevent premature
polymerization, given their inherent reactivity in the presence of free radicals and bases (Zhang
et al., 2018). Well-known stabilizers for cyanoacrylate monomers can be categorized into anionic
inhibitors and free radical inhibitors. Examples of free radical inhibitors include hydroquinone,
catechol, hindered phenols, and their derivatives. On the other hand, anionic inhibitors comprise
Lewis or protonic acids. Acidic gases like hydrogen fluoride, boron trifluoride, nitric oxide,
sulfur dioxide, and sulfur trioxide among others, are effectively employed in the manufacturing
process to prevent premature polymerization in distillation columns, pipes, and headspace (Xie et
al., 2022). This is because they can stabilize the cyanoacrylate monomer in both liquid and
gaseous phases. Other acidic compounds may also be utilized for this purpose.

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2.4 Condensation-DE polymerization Reaction to Produce Alkyl 2-Cyanoacrylate
In addition to the hydrocarbon-primarily based alkyl-2-cyanoacrylates highlighted in
advance, a diverse array of strong point mono and difunctional cyanoacrylate esters had been
meticulously synthesized via the condensation-DE polymerization response approach (Katti &
Krishnamurti, 1999). These compounds had been specially crafted to function adhesives with
particular and distinct houses. Allyl 2-cyanoacrylate, as an example, introduces allyl
functionality, providing exclusive adhesive traits that find packages in specialised bonding
conditions (Raja, 2016). Ethylene glycol di-2-cyanoacrylate, by means of incorporating ethylene
glycol as a di-purposeful unit, complements adhesive properties and introduces crosslinking
abilities, making it especially well-suited for programs requiring heightened bond power
(Pooresmaeil et al., 2022).. Neopentyl glycol di-2-cyanoacrylate, with neopentyl glycol as a di-
functional unit, contributes precise chemical and mechanical houses to the cyanoacrylate,
thereby increasing its range of applications in adhesive generation.
Dicyanoacrylate of poly (ethylene glycol), incorporating poly (ethylene glycol) as part of
its shape, enhances flexibility and compatibility with specific substrates, making it suitable for
various adhesive applications (Katti & Krishnamurti, 1999). Additionally, the inclusion of
thiocyano capability in Thiocyanoacrylates introduces precise chemical characteristics, probably

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offering superior adhesion houses and specialized packages in precise environments or with
specific substrates. The synthesis of these difunctional cyanoacrylates includes the condensation
response of suitable precursors, main to the formation of polymers with tailored properties
(Zhang et al., 2018). This diversification inside the cyanoacrylate family results in a broader
spectrum of adhesive alternatives, each possessing its very own awesome blessings and
programs. Researchers and enterprise specialists are actively engaged inside the exploration and
improvement of new formulations, aiming to meet unique adhesive necessities throughout
numerous fields (Katti & Krishnamurti, 1999). This non-stop innovation underscores the
dynamic nature of adhesive era and its pivotal role in diverse commercial and medical programs.

2.5 Acceleration of anionic polymerization of Cyanoacrylate-based adhesives By Sodium

hydrogen Carbonate (Baking powder)
The primary function or use of an accelerator is to facilitate quick setting and bond times,
however, it can be utilized to create gaps on the surface or increase the surface area for curing.
They also help by providing moisture to speed up the curing process of the cyanoacrylate-based
adhesives (Raja, 2016). In addition, are mostly significant in dry climates. Due to its high water
solubility and low vapour pressure, sodium hydrogen carbonate dissociates completely to sodium
(Na+) and bicarbonate (HCO3-) ions. It is low toxicity concern to aquatic organisms. When
bicarbonate is dissolved in water, a re-equilibration takes place as follows

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Resonance Stabilization of Negative Charge

Formation of the Resonance of Negative Charged anion

Formation of the Intermediate

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Copolymerization Structure
The two resilient electronegative (cyano and carboxyl) functional clusters initiate anionic
polymerization instigated by bases for instance water, and alcohols among others and leads to
greater molecular polymer through the carbanion. Polymerization is usually initiated by presence
of water or moisture, which is a weak base (Raja, 2016). Moisture avails the OH- which is basic
in nature; this initiates the anionic polymerization of the cyanoacrylate-based adhesive. On
addition of sodium bicarbonate (baking powder), it dissociates into Na + Cation and HCO3-anion.
Due to presence of moist characteristic bicarbonate ion, exist in an equilibrium state of CO 32- ion
and H+ ion (Zhang et al., 2021).The CO32- formed has t has four unpaired electrons compared to
OH- which has two unpaired electrons. Hence CO32- result a more electronegative intermediate
with carbanion with two unpaired electron and an oxanion with two unpaired electrons while
OH- gives an intermediate with carbanion having two unpaired electrons (Zhang et al., 2021).
Presence of four unpaired electrons give rise to double anionic polymerization at same
time ,however the intermediate with only two unpaired electron give rise to single
polymerization at a time.
2.6 Retardation effect of Citric acid on anionic polymerization of cyanoacrylate-based
adhesives
In each anionic and zwitterionic polymerization modes, the presence of robust acids
completely hinders the polymerization manner. The kinetics of the bottom-catalyzed solution
polymerization of cyanoacrylate-based adhesives has gone through good-sized investigation. The
said findings imply that in the absence of robust acids, polymerization lacks an intrinsic

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termination step, and the general kinetics is contingent on the initiation fees of diverse initiators
(Madurga et al., 2017). In the context of growing polymeric radicals, the energetic stop forms a
unique entity. Conversely, in ionically growing polymers, the energetic give up comprises two
species—a charged terminal atom or terminal group of the polymer, followed by using an
oppositely charged counter ion. The interplay between those entities may also lead to the
termination of polymerization, and this event can arise through diverse mechanisms (Zhang et
al., 2023). It is noteworthy that citric acid, represented as H3C6H507 (aq), is a susceptible
polyprotic acid generally discovered in result inclusive of oranges and lemons. Citric acid
undergoes a reaction with water, as illustrated underneath:

Dissolution Acidic Structure

H₃O⁺ + OH⁻ → 2H₂O

The interaction between the hydroxonium ion (H₃O⁺) and the hydroxyl ion (OH⁻)

C₆H₈O₇ (s) + H₂O (l) ⇌ C₆H₈O₇ (aq)

The dissolution of citric acid (aqueous)
By introduction aqueous citric acid, it is believed to retard the anionic polymerization of
cyanoacrylate-based adhesives, either by two steps; termination of polymerization by interaction

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of hydroxium ions and the intermediate radical or by reaction of the hydroxium ion by the
hydroxyl ion (base) to form water (Zhang et al., 2021). This is because of high reactivity nature
of the HO3+ ions (10). This reaction exemplifies the involvement of citric acid in a dynamic
chemical procedure, emphasizing its susceptible acidity and polyprotic nature. The durability of
the joint formed when exposed to water or a moist environment has a short life. They however
have an accelerated curing when used on cotton or wool substrate, leading to a burn or starting
fire. This has created concern on how to retard the process of polymerization, to help manage
curing occurring due to accidental spillage. Which may lead to burn or start a fire? Medical
research and studies have shown that cyanoacrylate-based adhesives cause irritation on human
skin and may also cause burns depending on the quantity. Importantly, this susceptible acid
contrasts with the strong acids referred to in advance that impede anionic and zwitterionic
polymerizations (Khare et al., 2021). The multifaceted nature of the termination steps in
polymerization underscores the significance of considering diverse chemical environments and
reacting species in these complicated procedures.
CHAPTER THREE: RESEARCH METHODOLOGY
3.1 Research Design
This research will employ experimental methods to determine the acceleration effect of
sodium bicarbonate (baking powder) and retardation effect of citric acid on anionic
polymerization of cyanoacrylate-based adhesives (Zhang et al., 2021). The cyanoacrylate-based
adhesive (Methyl-2-cyanoacrylate) will be sampled from Crystal Adhesives Ltd Manufacture in
Nairobi county. This will be realized by taking note of duration of anionic polymerization and
curing against percentage mixture content. A graph will be plotted to determine the trend in
anionic polymerization with variation in percentage of individual mixture content, both for
sodium bicarbonate and citric acid.
3.2 Sample size and Sampling Technique
Twenty-five (25g) of cyanoacrylate-based adhesive (methyl-2-cyanoacyrlate) will be
purchased from Crystal Adhesives Ltd Manufacture in Nairobi county. The study will commence
immediately the sample is obtained to minimize on time loose. A packet of baking powder will
be bought from whole sale retailer outside the school premises, while citric acid will be acquired
from the school laboratory. The contents (Adhesive and accelerator or retarder) will be mixed on
the surface of the substrate in the mass ratio, 1:1, 2:3, 1:4, 1:9 and control experiment. The

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duration taken for each mixture to cure will be measure with suitable Stopwatch. By using
weighing mass ranging from 25g to 1000g joint strength of the cured substrate will be determine
by the formula below;
F=Ma
Where; F = force that the cured joint can support.
M = weighing mass.
a = acceleration due to earth’s gravity.
3.3 Research Instruments
3.3.1 Apparatus
 Electric weighing balance
 Measuring cylinder
 Dropper
 20 Nails
 20,5cm x 5cm wood Planks ( with smooth surface)
 Stopwatch
 Spatula
 Gloves
 Stand and clamp
 Hammer
 Weighing Masses 25g-1000g
3.3.2 Reagents
 Distilled water
 100ml of 1M Citric acid
 50g of Sodium hydrogen carbonate (baking powder)
3.4 Data collection Procedure
1. Obtain 2, 5cm x 5cm x 1cm wood planks.
2. Hammer nail on the surface center of each wood plank
3. Clean the surfaces of the wood planks with clean dry piece of cloth.
5. Weigh 1g of sodium hydrogen carbonate (baking powder) on the weighing machine.
4. Put the weighed mass of sodium hydrogen carbonate on the opposite surface to the nailed

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 Side
5. Weigh 1g of Cyanoacrylate-based adhesive (methyl-2-cyanoacyrlate) (highly
recommended in vacuum setting to prevent immediate polymerization.
6. Pour the measured adhesive on top on the accelerator (sodium hydrogen carbonate) which
is on the surface of the wood plank.
7. Clamp the two wood planks together immediately and place them in vertical orientation.
8. Start the stopwatch immediately the clamping is done.
9. Take record time the mixture takes to cure and form firm joint between the two wood
planks.
10. After an hour set up a stand and clamp.
11. Suspend the clumped wood planks on the stand using nail on the surface (in horizontal
orientation).
12. Place different weighing masses, starting with Smallest which is 25g, until the joint
separates
13. Record the mass that the joint support prior separation.
14. Repeat the procedure with different adhesive /baking powder mixture in the proportion
of (1:1, 2:3, 1:4, and 1:9).
15. Set up a control experiment, using adhesive only.
16. Record your data in the tables below.
Mixture Content Adhesive 50 40 30 20 10
(%) NaHCO3 50 60 70 80 90
Curing Time (Sec)

Mixture Content Adhesive 50 40 30 20 10

(%) H3C6H507 50 60 70 80 90
Curing Time (Sec)

NOTE: Repeat the whole procedure using citric acid instead of Sodium hydrogen carbonate.

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The diagram above shows the arrangement of the requirements during the experiment
3.5 Data Processing and Analysis
The data will be processed and analyzed by plotting graph of Curing time against
percentage mixture content (adhesive and baking powder /citric acid). By observing the trend of
graph, the effect of the accelerator (Sodium hydrogen carbonate) and retardate (Citric acid) on
rate of Anionic polymerization will be established.

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3.6 Research Plan

Task Month
Research proposal writing January
Proposal presentation February
Commencement and conducting project work March
Final project presentation April

3.7 Research Budget

Items Cost (Ksh)
3 Methyl-2-cyanoacyrlate (super glue) 300
1 packet of Baking powder 200
20,5 cm x 5 cm x 1 cm wood planks 500
Citric acid 1L 500
Distilled water 1L 100
20 pieces of Nail 300
TOTAL 3700

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