AALTO UNIVERSITY

SCHOOL OF CHEMICAL ENGINEERING

Department of Chemical and Metallurgical Technology

CHEM-E7120 Laboratory project in chemical engineering

Date: 26.01.2024

Polycaprolactone (PCL)

Report no.: I

version 1

Group names: TAME

Waqar Ahmad Ali

Muhammad Abdul Wasayh
Hassan Mujtba
Imtiaz Alam
Umer Amin

26.01.2024
 Table of Content
Objectives of the Report ............................................................................................................................... 4
Hours Estimate:............................................................................................................................................. 4
Introduction .................................................................................................................................................. 5
Raw Materials and Product........................................................................................................................... 6
Specification and Grade ................................................................................................................................ 7
Cyclohexanone: ......................................................................................................................................... 7
Physical and Chemical Properties ......................................................................................................... 7
Epsilon-Caprolactone (ε-CL) ...................................................................................................................... 8
Physical and Chemical Properties ......................................................................................................... 9
Polycaprolactone .................................................................................................................................... 10
Physical and Chemical Properties ....................................................................................................... 10
Market Share & Economic Potential ........................................................................................................... 12
Market Share by Form ............................................................................................................................ 12
Market Share by Geography ................................................................................................................... 12
Pricing.......................................................................................................................................................... 14
Raw Material ........................................................................................................................................... 14
Product .................................................................................................................................................... 14
Plant Capacities ........................................................................................................................................... 14
Plant Location ............................................................................................................................................. 15
Process Alternatives.................................................................................................................................... 16
Polycondensation:................................................................................................................................... 16
Ring Opening Polymerization (ROP): ...................................................................................................... 17
Anionic ROP:........................................................................................................................................ 17
Cationic ROP:....................................................................................................................................... 17
Coordination-insertion ROP: ............................................................................................................... 18
Comparison of Process Alternatives: ...................................................................................................... 19
Polycondensation:............................................................................................................................... 19
Ring Opening Polymerization (ROP): .................................................................................................. 19
Evaluation Criteria: ................................................................................................................................. 20
Block Flow Diagram of the Process. ............................................................................................................ 21
SAFETY AND ENVIRONMENTAL PRECAUTIONS .......................................................................................... 22
Cyclohexanone: ....................................................................................................................................... 22
Flammability:....................................................................................................................................... 22
 Toxicity: ............................................................................................................................................... 22
Environmental Hazards: ...................................................................................................................... 22
Reaction Hazards: ............................................................................................................................... 22
Storage & Handling: ............................................................................................................................ 22
Peracetic Acid:......................................................................................................................................... 23
Flammability:....................................................................................................................................... 23
Toxicity: ............................................................................................................................................... 23
Environmental Hazards: ...................................................................................................................... 23
Reaction Hazards: ............................................................................................................................... 23
Storage & Handling: ............................................................................................................................ 23
ε-Caprolactone ........................................................................................................................................ 24
Flammability:....................................................................................................................................... 24
Toxicity: ............................................................................................................................................... 24
Environmental Hazards: ...................................................................................................................... 24
Reaction Hazards: ............................................................................................................................... 24
Storage & Handling: ............................................................................................................................ 24
Polycaprolactone: ................................................................................................................................... 25
Flammability:....................................................................................................................................... 25
Toxicity: ............................................................................................................................................... 25
Environmental Hazards: ...................................................................................................................... 25
Reaction Hazards: ............................................................................................................................... 25
Storage & Handling: ............................................................................................................................ 25
Material and safety datasheet (MSDS) and NFPA guide for hazard ratings: .............................................. 26
PERACETIC ACID: ..................................................................................................................................... 26
Cyclohexanone: ....................................................................................................................................... 27
Polycaprolactone: ................................................................................................................................... 28
ε-caprolactone: ....................................................................................................................................... 28
References .................................................................................................................................................. 29
Objectives of the Report
The Objective of this First report to evaluate technical and economic feasibility of Polycaprolactone (PCL)
production. For a reliable estimation, a wide range of aspects has been investigated. Studying the product
market in the early stages of the project is imperative. Thus, the information related to the market, market
share, raw materials and product prices was gathered from available resources. Then, comparison for the
selected production routes was performed based on technical, economic, environmental, and safety
evaluations. Also, Safety and environmental studies were conducted for substances involved in the
production process. The most promising candidate went under a more comprehensive study. Accordingly,
mass and energy balance were performed. Experimental studies will be performed later in the course to
compare and validate the theoretical results.

Hours Estimate:
Steps Hours Used
WAA HM MAW UA IA
Lab. project start up 1 1 1 1 1
Market study 1 1 5 2 1
Process alternatives 5 3 1 1 1
Comparison of alternatives 5 5 1 1 1
Simple Process flow diagrams 2 4 1 1 1
Env. & safety assessments 1 0 0 0 6
Material balance & Simulation 0 2 0 0 0
Plant location 1 1 6 1 0
Report I correction 3 1 1 1 1
Report I total 19 18 16 8 12
 Introduction
Polycaprolactone (PCL) is a polymer, an aliphatic polyester, made from Hexanoate monomer. It is a
semicrystalline polymer having a degree of polymerization reaching around 69% (Labet & Thielemans
2009). PCL is an important polymer due to its mechanical properties, biodegradability and it ability to br
miscible with a large number of other polymers. It’s different properties such as mechanical, physical and
thermal properties rely on its molecular weight and crystallinity.

PCL is a biodegradable polyester having a low melting point around 60 ˚C and a glass transition
temperature of -60 ˚C. PCL Biodegrades in several months to several years which depends on the its
degree of crystallinity and the conditions of degradation.

Due to interesting properties of PCL such as controlablity, biodegradability, ability to be made from
renewable resources and miscibility with other polymers, it has a wide variety of applications. It degrades
by the hydrolysis of its ester in physiological conditions such as in human body, and therefore is considered
to be used in implantations in medical field.

The Structure of PCL is shown below in the diagram (McKeen, 2021).

Figure 1- Structure of PCL (McKeen, 2021).

Raw Materials and Product
Raw materials for polycaprolactone production depend on the pathway used. There are two main
processes to produce polycaprolactone, polycondensation of a hydrocarboxylic acid (6-hydrohexanoic
acid) and the ring-opening polymerization (ROP) of a lactone known as ε-caprolactone (ε-CL). The
production technique of our interest is the ring-opening polymerization. It should be clear that ε-
caprolactone (ε-CL) is considered as a raw material for the polycaprolactone (PCL). However, ε-
caprolactone (ε-CL) itself is a monomer and this monomer is formed from the cyclohexanone. The overall
process of conversion of cyclohexanone to ε-Caprolactone (CL) is called Beckmann rearrangement
followed by lactonization.

The Chemical Equations to produce polycaprolactone are as following;

1. Oxidation of Cyclohexanone-to-Cyclohexanone Oxime:

Cyclohexanone + H2O.amine → Cyclohexanone Oxime

2. Beckmann Rearrangement
Cyclohexanone Oxime → Epsilon-Caprolactam

3. Lactonization (cyclization to form ε-Caprolactone)

Epsilon-Caprolactam → Epsilon-Caprolactone

4. Polymerization
n ε-Caprolactone → (-C(O)O-)n

Based on the process, we can define Cyclohexanone as the principle raw material, Epsilon-Caprolactone
(ε-CL) as the intermediate product, and Polycaprolactone as the main product.

(Marianne Labet, 2009)

A variety of catalytic systems are present. The catalysts used in this process is Tin-octoate and n-hexanol.
Specification and Grade
Cyclohexanone:
Cyclohexanone is also known as oxocyclohexane, cyclohexyl ketone and pimelic ketone. It is a clear oily
liquid with pungent odour and has a colorless to light yellow tinge. Its molecular formula is C6H10O. Crude
oil is a natural source of cyclohexanone. It reacts with oxidants i.e., nitric acid.

(https://pubchem.ncbi.nlm.nih.gov/compound/Cyclohexanone, n.d.)

Physical and Chemical Properties

Property Name Property Value
Cas Number 108-94-1
Molecular weight 98.14 g/mol
Topological polar surface area 17.1Ų
Heavy atom count 7
Complexity 68.2
Flashpoint 111°F / 43.9
Boiling point 312.1 ° F / 155.6 at 760 mm Hg
Melting point 3 ° F/ -16.1 ° C
Vapour pressure 101.7° F at 10 mm Hg
Water solubility 50 to 100 mg/mL at 64° F
Density 0.945 at 68 °F

Property Value/Description
NFPA Health 1 (Can cause significant irritation)
Rating
Health Inhaled: Irritation of throat and respiratory passages, headaches, and nausea.
Hazards Excessive exposure to the eyes, nose, and skin can cause irritation, drowsiness, and
unconsciousness.
NFPA Fire 3 (Can be ignited under all ambient temperature conditions)
Rating
Fire Hazards Heat, sparks, or flames can ignite; vapors are heavier than air and may travel to the
source of ignition and surrounding areas. Low flash point.
Instability 0 (Normally stable, even under fire conditions)
Rating
 Spill Isolate the leak to a minimum of 50 meters. Prevent spreading into waterways,
Response sewers, and basements. Soak up spillage with dry materials like dirt or combustible
materials.
Firefighting Alcohol-resistant foam, dry chemical, or CO2. Remove all ignition sources.
Agents
PPE Use personal protective equipment (PPE) like gloves and goggles when handling.
Equipment Remove contaminated clothing immediately.
Storage Store in a cool, dry, well-ventilated area free from the risk of ignition.
Conditions
Transportatio Can be transported in drums and/or tank trucks. Falls into packing group III, hazard
n class III. Highly flammable and an irritant.
(Products, n.d.)

Epsilon-Caprolactone (ε-CL)
ε-Caprolactone is a colorless liquid. It is soluble in benzene, alcohol, water, and other polar solvents etc.
However, it is insoluble in liquids i.e., Sherwood oil. The chemical formula is C6H10O2. Due to the property’s
biocompatibility and biodegradability, ε-caprolactone is used for 3D printing, drug carrier, and medial
appliances etc. It is used at many applications such as acrylic resins, polyester, polyurethane, epoxy resin
and coatings to enhance flexibility.

(Caprolactone Compound, n.d.)

Typical chemical reactions of ε-Caprolactone are;

(Products - Epsilon-Caprolactone, n.d.)

Physical and Chemical Properties

Property Value/Description
CAS 502-44-3
Molecular mass 114.2 g/mol
Boiling point 237°C
Melting point -1.5°C
Density 1.07 g/cm³
Solubility in water miscible
Vapor pressure at 25°C 0.8 Pa
Relative vapor density 3.9
Flash point 127°C
Auto-ignition temperature 204°C
Explosive limits vol% in air 1.2-9
Octanol/water partition coefficient as log Pow 0.68

ACUTE HAZARDS PREVENTION FIRE FIGHTING

Fire & Combustible. NO open flames. Use powder, alcohol-
Explosion resistant foam, carbon
dioxide, and water spray.
In fire occurs keep drums,
etc., cool by spraying with
water.
 Area Symptoms Prevention First AID
Inhalation Use ventilation. Fresh air, rest.
Skin Protective gloves. Rinse skin with plenty of
water or shower.
Eyes Redness. Pain. Wear safety goggles. Rinse with plenty of water
(remove contact lenses if
easily possible). Refer for
medical attention.
Ingestion Do not eat, drink, or smoke Rinse mouth.
during work.
(epsilon-CAPROLACTONE, 2009)

Polycaprolactone
PCL, a synthetic polyester with partial crystallinity, exhibits a low melting point of 60°C and a glass
transition temperature of −60°C. Its production involves the ring-opening polymerization of ε-
caprolactone. PCL is easily degradable by microorganism lipases and Esterases. Structurally, PCL bears
similarity to cutin.

(N.R. Nair, 2019)

Physical and Chemical Properties

Property Value/Description
CAS 24980-41-4
Molecular mass 114.14 g/mol
Boiling point 237°C
Melting point 60°C
Density 1.146 g/cm³
Vapor pressure at 25°C 0.13 mm Hg
Relative vapor density 3.9
Flash point 127°C
(Dictionary EN > P > 24980-41-4, n.d.)
 Properties Description
Biocompatible (i) Nonimmunogenic
(ii) Nontoxic
Porosity (i) Ideal porosity ≈ 90%
(ii) Allows the infiltration of
cells and nutrients
(iii) Removal of waste
products
(iv) Greater surface area for
cell attachment and
proliferation
Biodegradable (i) Temporary structure for
the attachment and
proliferation of cells
(ii) Degrades as new bone is
deposited
(iii) Eliminating the need for
further invasive surgery
(iv) Degradation products are
non-toxic and easily secreted
through metabolic pathways
Osteoconductive Support bone growth and
encourage ingrowth of
surrounding bone
Mechanical properties (i) Stable for surgical handling
(ii) Able to withstand the
forces exerted by the body
(A K Bassi 1, 2021)
Market Share & Economic Potential
The polycaprolactone market is growing steadily due to the number of applications and desired favorable
properties. The international market is looking for more biodegradable materials for various applications
i.e., automobile industry, healthcare sector, packaging industry, electronics etc.

(polycaprolactone-market, n.d.)

According to report of “Verified Market Research,” the polycaprolactone market size in the year 2022 was
valued at 1.14 billion US Dollars. Moreover, VMR reported the size of the market growing with the 5.5%
rate by 2030 (around 1.75 billion US Dollars). This global Polycaprolactone Market is experiencing
substantial growth due to its widespread use in thermoplastic polyurethane production. The surge in
polyurethane demand is a key factor fueling this expansion.

Market Share by Form

Polycaprolactone market involves following forms of PCL being sold for various applications

1. Pallets
2. Nanosphere
3. Microsphere
Out of all these 3 forms, pallets hold the biggest ratio in the market. This is because the pallets are used
as a raw material for thermoplastic polyurethane production.

Market Share by Geography

Dividing the geography of earth into 4 main sections;

1. Europe
2. Asia Pacific
3. North America
4. Rest of the Region

Based on the development and usage, Asia Pacific stands as the largest market for PCL. Moreover, Asia is
expected to stay the largest marketplace for PCL during the forecast period till 2030. The most crucial
factors holding Asia as the biggest marketplace are as following;
 1. Large Chemical Industry
2. Adoptability for advanced techniques and processes
3. Increasing industrialization to meet the demand
Some of the major groups leading in the market of PCL are as following;

1. Erstorp
2. Daicel
3. Esun, BASF SE
4. Durect Corporation
5. Sigma-Aldrich Corporation
6. Shenzhen Esun Industries
7. Corbion Purac
8. Polysciences Inc
Besides the number of groups leading the PCL market, the demand due to the industrial growth creates
an equal opportunity to dive into the PCL market competition using various strategies. Porter's five forces
model serves as a valuable tool for evaluating the competitive dynamics within the Global
Polycaprolactone Market. It aids in assessing the attractiveness of specific sectors and determining
investment opportunities.

1. Competitive Rivalry
2. Bargaining power of buyer
3. Bargaining power of suppliers
4. Threat from new entrants
5. Threat of substitutes
(Chemical & Material>Advanced Materials>Polycaprolactone Market, 2022)
Pricing
Raw Material
Marketprice of raw material cyclohexanol is in US Dollars/Metric Ton (June 2023) is presented in the table.
The cost of the raw material varied all over the world.

Region Price USD/Ton

Europe $ 1828-1910
Asia Pacific $ 1417
North America $ 1681
Other Countries $ 1520
(Chemical Prices - Cyclohexanone, n.d.)

Product
Region Price USD/Ton
Europe $ 2470
Asia Pacific $ 2110
North America $ 2350
Other Countries $ 2320

Plant Capacities
Based on the available data, we can take an average of the price of polycaprolactone. And as we know,
know the annual sales of the PCL. We can calculate the overall worldwide production of PCL.

Production = Total sale/Price per ton

Production = 1.14 billion USD / 2,312 USD per ton

Production = 0.493 million tons of PCL

Plant Location
Setting up a plant of PCL in Finland depends on various parameters. These parameters play a crucial role
as the production cost, maintenance cost, transportation, supply chain and cost of services etc, everything
depends on the location. Some of the factors that play the crucial role in this decision are as follows.

1. Land cost:
The cost of acquiring land for setting up a plant, availability of services at that location, road network are
especially important parts. The right selection of an industrial zone can save the fixed investment cost.

2. Connectivity:
Connectivity means established road and rail network, communication network, airport, and seaport
nearby for the transportation of humans and goods.

3. Raw material:
Raw material should be easily available and can be easily transported to the plant site.

4. Availability of the services:

Services include electricity, water supply, and clean air etc. This is especially important for setting up a
plant to have a sustainable life for the personnel on the site and to keep the plant running without any
interruption.

5. Labor Force:
Evaluate the availability of skilled labor in the region for the plant. The plant should be easily reachable
and should have convenient transportation.

6. Environmental conditions:
The weather, land situation, waste handling and clean air are some of the important major factors that
must be considered for setting up a plant.

Based on such factors, the location should be selected. Considering all these factors and looking for a
feasible plant location there are some industrial zones that can be selected for feasibility study for
commissioning of a plant. Some of these locations in Finland are Porvo, Kotka-Hamina Industrial Zone,
Pori Industrial Area, and Tampere Region Industrial Zones. These industrial zones relate to the road
network to ease the transportation from seaports to the industrial site. Airports in the vicinity, rail and
road network enable easy commute for the labor. The availability of services like water, air, electricity,
and fuel is also advantageous. The final decision should be made considering the government rules and
regulations and the cost-effective location for the plant.
Process Alternatives
Polycaprolactone (PCL) is non-hazardous aliphatic polymer. Although it is not very new polymer and have
been researched upon decades earlier, but recently it has got the attention worldwide again due to its
unique properties of biodegradability and other physical and mechanical properties. Due to the recent
advancement in the conservation of our environment, researchers are now again putting an effort to
commercialize the use of biodegradable polymers. As PCL is a biodegradable polymer it has a lot of
potential to be used in different industries commercially.

PCL can be produced commercially by two methods, Polycondensation of 6-hydroxyhexanoic acid and
Ring Opening Polymerization (ROP) of ε-caprolactone.

Both ε-caprolactone and 6-hydroxyhexanoic are intermediary products produced by the oxidation of
cyclohexanol. Industrially, ε-caprolactone is produced by the oxidation of cyclohexanone with peracetic
acid. (Labet & Thielemans 2009).

Polycondensation:
Polycaprolactone produced via polycondensation of 6-hydroxyhexanoic acid. In this method 6-
hydroxyhexanoic acid with a suitable catalyst under vacuum to continuously remove the water that is
being produced during the polycondensation reaction. The reaction usually takes several hours to
complete and the temperature range is from 80 ˚C to 150 ˚C.

Figure 2- Polycondensation to produce PCL (Labet & Thielemans 2009).

PCL Produced through polycondensation has lower molecular weight, low polydispersity and a low-quality
polymer (Labet & Thielemans 2009).
Ring Opening Polymerization (ROP):
As opposed to polycondensation, ring opening polymerization (ROP) produce a higher molecular weight
polymer, low polydispersity with a good quality (Labet & Thielemans 2009), therefore it is preferred
commercially.

In ROP, there are three types of catalysts that can be used which further divide this process into three
categories.

Anionic ROP:
In this method different alkali metal salts such as t-BuOK, KH, PhLi and others are used. The ring opens
only in the acyl-oxygen positions in this anionic polymerization and anionic specie attacks the carbon of
the monomer and an alkoxide specie is formed. The main drawback of this method is the occurrence
phenomenon known as transesterification also called back-biting, which happens in the later stages of the
polymerization. If the polymerization is not stopped before back-biting the resulting product would have
a lower molecular weight or cyclic polymerization.

Cationic ROP:
In this method of ROP, a positively charged specie is formed on which carbonyl group of monomer attacks
which caused the positively charged specie to open the ring trough bimolecular nucleophilic substitution
(SN2) reaction. The catalyst that are often used in this reaction are hetero-scorpionate aluminum
complexes, mono- and bis(phosphino-phenolate) aluminum cationic complexes, Trityl tetrafluoroborate
(Ph3CBF4) [30], and iron (III) chloride (FeCl3) or FeCl3/nH2O systems (Gizem Özge Kayan and Asgar Kayan,
2023).

Cationic ROP is a difficult reaction to control and often results in low molecular weight polymer or
oligomer (Gizem Özge Kayan and Asgar Kayan, 2023).
Coordination-insertion ROP:
Coordination-insertion ROP is the most common form of ring opening polymerization. It is actually a
pseudo-anionic ROP. As illustrated below in the schematic diagram, the ε-caprolactone monomer first
binds to the center of metal by carbonyl-oxygen atom. The nucleophilic alkoxide group of the catalyst
then coordinated to the activated carbonyl-group of the monomer which results in the cleavage of the
acyl-oxygen bond. After this the monomer binds to the metal center and inserted into the metal-alkoxide
bond which results in the formation of polycaprolactone PCL. The most common catalyst used her is the
Tin-Octoate.

Figure 3- Coordination- insertion to produce PCL (Gizem Özge Kayan and Asgar Kayan, 2023).
Comparison of Process Alternatives:
Below are some of the factors that are needed to be considered for the comparison of the processes
available and to choose a most feasible process for the production.

• Operation principle of processes

• Advantages and disadvantages (such as capability of producing the required quality, raw material
and energy efficiency, waste generation, safety, and cost data)
• Status of the method in the market and novelty (modern vs. old fashion), number of process
references
• Availability and cost of the reactants, as well as the desired yield and purity of the PCL product

Polycondensation:
• Operating Principle: PCL is produced by polycondensation of 6-hydroxyhexanoic acid under
vacuum, thereby removing the water produced during the reaction and displacing the equilibrium
towards the formation of the polymer (Labet & Thielemans 2009).
• Advantages: the controllability of the reaction is very difficult.
• Disadvantages: Yields a low molecular weight PCL and quality product.
• Status of the Method: The Method is well known in the market for different polymer products.

Ring Opening Polymerization (ROP):

• Operating Principle: (Coordination-insertion ROP) the ε-caprolactone monomer first binds to the
center of metal by carbonyl-oxygen atom. The nucleophilic alkoxide group of the catalyst then
coordinated to the activated carbonyl-group of the monomer which results in the cleavage of the
acyl-oxygen bond. After this the monomer binds to the metal center and inserted into the metal-
alkoxide bond which results in the formation of polycaprolactone PCL.
• Advantages: Yields a good quality of the product with high molecular weight PCL.
• Status of the Method: The method is well known in the market and is the most common method
being used in the production of polycaprolactone PCL.
Evaluation Criteria:
To evaluate process, a comparison is made as suggested in the instructions.

Method Polycondensation Ring opening polymerization ROP

Economics
Safety Aspects
Environmental Ethanol Water
Aspects
Technical 80 to 150 ˚C, Under Vacuum, low 80 to 150 ˚C, Low pressure, High Efficiency,
Aspects efficiency, high energy consumption, Low energy Consumption, Reliable, Flexible
not flexible
Maturity or The process is mature and well known The process is well known and mature and
Novelty of the most common for the production of PCL
Process

Next on the basis of above table we can justify the selection by giving points to different aspects and then
choosing the process with highest Score.

Process Alternatives A B Justification

Polycondensation Ring Opening
Polymerization
Criteria Weig Points total Points Total
ht
Technical 3 2 6 5 15 Both methods operate at around
feasibility same temperature and different
pressure, but method B is more
reliable and has high efficiency
Economic 5 2 10 4 20 Method B produces a good quality of
viability product.
Yield 3 1 3 4 12 Method B has a higher yield of
producing PCL
Environmental 4 3 12 4 16 Both methods produce waste and but
Impact B has side product of water while A
may produce ethanol.
Safety 4 4 16 5 20 Reactants used in both methods
hazardous and toxic
Scale-up 3 3 9 5 15 There are a many process references
(maturity) for method B and it is being
commonly used in industry, however
method A is less preferred
Total 22 56 98
Score 2.54 4.45 Based on the given justification and
scores, method B is the best
proposed method
 Block Flow Diagram of the Process.
Simplified Block flow diagram of Polycaprolactone PCL production process starting from Baeyer Villiger
oxidation of cyclohexanone to the production of polycaprolactone PCL is shown below.

Catalyst
n-Hexanol (R-OH)
Preparation
Tin-Octoate unit

Oxygen
Tin-Alkoxide

Oxidation Polymerization Product

Cyclohexanone
Reaction Unit (80 to 150 ˚C) Purification

Ε-caprolactone Polycaprolactone

Product Pure PCL

Storage
SAFETY AND ENVIRONMENTAL PRECAUTIONS
Cyclohexanone:
Cyclohexanone is a colorless liquid with a sweet, pleasant odor. It is a cyclic ketone, meaning it has a
ketone functional group (C=O) located in a ring of six carbon atoms. Cyclohexanone is miscible with water
and most organic solvents. This chemical is considered hazardous by the 2012 OSHA Hazard
Communication Standard (29 CFR 1910.1200)

Flammability:
The substance is classified as a flammable liquid and vapor, posing risks of fire and combustion. It should
be stored away from heat, sparks, open flames, and hot surfaces. Smoking should be prohibited in areas
where the substance is handled. Proper ventilation and non-sparking tools should be used to minimize
the risk of ignition.

Toxicity:
Cyclohexanone can cause skin irritation, serious eye damage, respiratory irritation, and may induce
drowsiness or dizziness. Ingestion, skin contact, or inhalation of the substance can result in harmful effects.
Protective equipment such as gloves, clothing, eye protection, and face protection should be worn when
handling the substance to prevent exposure.

Environmental Hazards:
The substance may pose environmental hazards if released into the environment. Proper disposal
methods should be followed to prevent contamination of soil, water, or air. Spills should be contained
and cleaned up promptly using appropriate methods and equipment to prevent environmental damage.

Reaction Hazards:
Cyclohexanone may react with certain chemicals or materials, leading to hazardous reactions. It is
important to avoid mixing it with incompatible substances and to handle it with caution to prevent
accidental reactions. Compatibility with other chemicals and materials should be assessed before storage
or use.

Storage & Handling:

The substance should be stored in tightly closed containers in a cool, well-ventilated area away from
incompatible materials. Proper labeling and handling procedures should be followed to prevent accidents
or exposure. Safety measures, including the use of protective equipment and adherence to safety
protocols, should be implemented during storage, handling, and disposal to minimize risks to health and
safety.
Peracetic Acid:
Flammability:
The substance is classified as a combustible liquid, and heating may lead to fire hazards. It should be kept
away from heat, sparks, open flames, and hot surfaces. Smoking should be strictly prohibited in areas
where the substance is handled. Proper ventilation is necessary to minimize the risk of ignition.

Toxicity:
The substance causes severe skin burns and eye damage and may cause respiratory irritation. It is harmful
if swallowed or inhaled. Personal protective equipment such as gloves, protective clothing, eye protection,
and face protection should be worn when handling the substance to prevent exposure.

Environmental Hazards:
The substance is very toxic to aquatic life, posing significant environmental hazards. Proper disposal
methods should be followed to prevent contamination of soil, water, or air. Spills should be contained
and cleaned up promptly using appropriate methods and equipment to prevent environmental damage.

Reaction Hazards:
The substance may react with certain chemicals or materials, leading to hazardous reactions. It is
important to avoid mixing it with incompatible substances and to handle it with caution to prevent
accidental reactions. Compatibility with other chemicals and materials should be assessed before storage
or use.

Storage & Handling:

The substance should be stored in a cool, well-ventilated area away from heat, sparks, open flames, and
sources of ignition. Containers should be kept tightly closed, and it should be stored away from other
materials. Special precautions should be taken to prevent exposure during handling, and personal
protective equipment should be used. Proper labeling and handling procedures should be followed to
prevent accidents or exposure. Safety measures should be implemented during storage, handling, and
disposal to minimize risks to health, safety, and the environment.
ε-Caprolactone
Flammability:
The substance exhibits no explicit flammability hazards based on the provided information. However,
precautionary measures should still be taken to avoid exposure to heat, sparks, and open flames to
prevent potential fire hazards during storage and handling.

Toxicity:
Regarding toxicity, the substance poses certain risks, especially causing serious eye irritation, as noted in
the provided hazard statements. It is crucial to handle the substance with care to prevent skin and eye
contact, which could lead to irritation or damage. Adequate personal protective equipment should be
worn to minimize the risk of exposure.

Environmental Hazards:
While there is no direct information provided regarding specific environmental hazards, precautions
should be taken to prevent the substance from entering drains or contaminating the environment. Spills
should be promptly cleaned up and disposed of properly to avoid environmental contamination.

Reaction Hazards:
Information on specific reaction hazards is not provided. However, it is generally advisable to avoid mixing
the substance with incompatible materials to prevent potential hazardous reactions. Compatibility with
other chemicals and materials should be assessed before storage or use.

Storage & Handling:

Proper storage and handling procedures are essential to ensure safety. The substance should be stored in
tightly closed containers in a cool, well-ventilated area, away from heat sources and incompatible
materials. Adequate ventilation should be maintained, and personnel should be trained in safe handling
practices to minimize risks associated with the substance.
Polycaprolactone:
Flammability:
The substance is not classified as flammable based on the information provided. However, precautions
should still be taken to prevent exposure to heat, sparks, or open flames during storage and handling to
avoid potential fire hazards.

Toxicity:
The substance is considered non-hazardous according to classification standards. Nonetheless, basic first-
aid measures are recommended for potential exposure scenarios, emphasizing the importance of seeking
medical attention if symptoms occur.

Environmental Hazards:
No specific environmental hazards are identified for the substance. However, general precautions are
advised to prevent its release into the environment, and appropriate containment and cleanup measures
should be implemented in case of spills to mitigate potential environmental impact.

Reaction Hazards:
Information regarding potential reaction hazards is not provided. Nonetheless, it is advisable to handle
the substance with care and to avoid mixing it with incompatible materials to prevent hazardous reactions.
Compatibility with other substances should be assessed before storage or use.

Storage & Handling:

Precautions for safe storage and handling include preventing the formation of combustible dusts, ensuring
adequate ventilation, and storing the substance in closed containers in dry, cool, and well-ventilated areas.
Proper handling procedures and personal protective equipment should be used to minimize risks
associated with the substance.
Material and safety datasheet (MSDS) and NFPA guide
for hazard ratings:
PERACETIC ACID:
Peracetic acid synonium Acetic peroxide, Peroxyacetic acid, Acetyl hydroperoxide having ICSC 1031
presents significant safety and environmental hazards due to its properties as a strong oxidizing
agent. Classified as a flammable liquid with a flash point of 62°C, it can generate explosive vapor-
air mixtures. Moreover, peracetic acid is corrosive, capable of causing severe skin burns and eye
damage upon contact. Inhalation or ingestion may lead to respiratory irritation and potential
harm to internal organs. Additionally, it poses a substantial threat to aquatic life.

To minimize risks associated with peracetic acid, meticulous handling is essential, adhering
closely to safety guidelines outlined in the Material Safety Data Sheet (MSDS) and International
Chemical Safety Cards (ICSC). These measures encompass avoiding direct contact with skin, eyes,
and clothing, refraining from inhaling vapors or mist, conducting operations in well-ventilated
spaces, and storing the substance in cool, dry, and shaded areas away from heat, sparks, and
open flames. Immediate medical attention is imperative in the event of exposure to peracetic
acid.

Peracetic acid is also a hazardous substance under the National Fire Protection Association
(NFPA) hazard classification system. The NFPA hazard ratings for peracetic acid are as follows:

• Health: 3
• Flammability: 2
• Instabilty: 4
• Physical hazards: OX

Fig source: https://cameochemicals.noaa.gov/chemical/5112

https://www.fishersci.com/store/msds?partNumber=AC257750250&productDescription=
PEROXYACETIC+ACID%2C+CA.35+25ML&vendorId=VN00032119&countryCode=US
&language=en
Cyclohexanone:
Cyclohexanone, synonym Ketohexamethylene, Pimelic ketone, Cyclohexyl ketone having ICSC: 0425
characterized as a flammable liquid with a flash point of 46°C (114.8°F), poses several hazards upon
exposure. It can irritate the skin, eyes, and respiratory system, leading to potential drowsiness or
dizziness. The substance is labeled with various hazard statements, highlighting its flammability and
capacity to cause skin irritation, serious eye damage, respiratory irritation, and drowsiness if swallowed,
in contact with skin, or inhaled. Precautionary measures include keeping away from heat, sparks, and
open flames, ensuring usage in well-ventilated areas, avoiding inhalation of vapor or mist, and wearing
protective gear such as gloves, clothing, eye protection, and face protection. In the event of exposure,
immediate first-aid measures involve washing the affected area with soap and water, rinsing the eyes
for at least 15 minutes, moving to fresh air if inhaled, and seeking medical attention if symptoms arise.
Fire-fighting methods include the use of water spray, carbon dioxide (CO2), dry chemical, or alcohol-
resistant foam, while accidental spills should be managed with absorbent material and disposed of in
compliance with local regulations. Storage guidelines recommend storing in a cool, dry place with tightly
closed containers, away from incompatible materials. Environmental precautions emphasize the
importance of static discharges and should not be directly drawn into environment as well do not flush
on ground.

Peracetic acid is also a hazardous substance under the National Fire Protection Association
(NFPA) hazard classification system. The NFPA hazard ratings for cyclohexanone are as follows:

• Health: 1
• Flammability: 2
• Instability: 0
• Physical hazard: N/A

Fig source: https://cameochemicals.noaa.gov/chemical/3044

https://www.fishersci.com/msdsproxy%3FproductName%3DC5504%26productDescription%3DCYCLOH
EXANONE%2BPURIFIED%2B4L%26catNo%3DC550-
4%26vendorId%3DVN00033897%26storeId%3D10652
Polycaprolactone:
Polycaprolactone, is classified as non-hazardous, as indicated by its Hazards Identification statement in
msds. This classification suggests that it does not present significant risks to health or the environment
under typical conditions of use. However, prudent precautions should still be observed to maintain safety.
But proper ventilation in areas where Polycaprolactone is handled, appropriate personal protective
equipment used, and practicing good hygiene practices such as thorough handwashing after contact. It's
crucial to keep the substance out of drains to protect the environment, especially water habitats. This
means we need to dispose of it properly and act fast if there's a spill to avoid harming nature. The
International Chemical Safety Card (ICSC) number for Polycaprolactone is 1741. NFPA is not issued rating
for polycaprolactone because it has biodegradable polyster used for various applications.

ε-caprolactone:
ε-caprolactone, also known as 6-Hexanolactone or 2-Oxepanone, is classified as hazardous according to
the 2012 OSHA Hazard Communication Standard (29 CFR 1910.1200). Precautionary measures include
thorough washing of exposed skin, wearing eye and face protection, and seeking medical attention in case
of contact with eyes or skin. Inhalation should be avoided, and medical attention sought if symptoms
occur. In case of ingestion, vomiting should not be induced, and medical attention is necessary. Specific
hazards include its flammability and the release of hazardous combustion products like carbon monoxide
and dioxide. Environmental precautions advise against letting the chemical enter the environment, and
proper containment and cleanup methods should be employed in case of spills. Handling and storage
require personal protective equipment, adequate ventilation, and avoidance of contact with incompatible
materials. The substance is irritating to the eyes and may have delayed or chronic effects, although specific
information on sensitization and carcinogenicity is not available.

The NFPA hazard ratings for Epsilon-caprolactone are as follows:

• Health: 3
• Flammability: 1
• Instability: 0
• Physical hazards: N/A

https://www.szabo-scandic.com/pub/media/product_data/msds/SAC/SAC-MSDS-SACSC-357410.pdf
References
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review’, Chemical Society Reviews, vol. 38, no. 12, p. 3484.
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4%26vendorId%3DVN00033897%26storeId%3D10652
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357410.pdf
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