Introduction to polymer science

EXPERIMENT NO: 10
Poly-Methyl Methacrylate

 AIM:
 To carry out the polymerization of methyl methacrylate (MMA) using appropriate techniques
to achieve a desired molecular weight and polymer structure.

 APPARATUS:
1. Round-bottom Flask: For the reaction mixture.
2. Heating Mantle or Hot Plate: For controlled heating of the reaction mixture.
3. Magnetic Stirrer: To ensure proper mixing of the reactants.
4. Condenser: To prevent the loss of volatile components and allow for refluxing.
5. Pipette: For precise addition of reagents.
6. Thermometer: For monitoring reaction temperature.
7. Burettes: For accurate measurement of liquids.

❖ CHEMICALS:
• Benzoyl Peroxide
• Acetone
• Methyl methacrylate (MMA)

 Chemical Reaction:
The production of Poly-methyl-methacrylate (PMMA) typically involves the free radical polymerization
of methyl methacrylate (MMA).
Chemical formula-
(C5H8O2)n

The synthesis of poly-methyl methacrylate (PMMA) involves the polymerization of methyl methacrylate
(MMA) through a free radical mechanism. Here’s a breakdown of the chemical reaction:
1. Monomer Structure
 Methyl Methacrylate (MMA):
(C4H8O2)n
2. Polymerization Process
The overall reaction can be simplified as follows:
1. Initiation: An initiator decomposes to form free radicals.
Initiator →Free Radical
Propagation: The free radical reacts with a molecule of MMA to initiate the polymerization:

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R∙+MMA→R-MMA
where R-MMA is a radical species that continues to react with additional MMA molecules.
2. Continued Chain Growth: The radical continues to add MMA units, forming a growing polymer
chain:
R-MMA∙+MMA→R-MMA-MMA
Termination: The polymerization ends when two radical chain ends combine:
R-MMA∙+R-MMA∙→PMMA

3. Overall Reaction Equation

The overall reaction can be summarized as:
n (C4H8O2)n → heat initiator (C4H8O2)n

where, n represents the number of MMA monomers that have reacted to form the polymer chain.

MMA BENZOYL PEROXIDE PMMA

+ 

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 Theory:

Poly-methyl methacrylate (PMMA) is a polymer that is widely used in various applications due to its
favorable properties. Here’s a breakdown of the theoretical aspects surrounding PMMA:
1. Chemical Structure:
Monomer: PMMA is derived from the polymerization of methyl methacrylate (MMA), a clear, colorless
liquid. Its chemical structure includes a methacrylate functional group, which contributes to its
reactivity.
Polymerization: The process typically involves free radical polymerization, where radicals initiate the
reaction, causing MMA molecules to link together to form long chains.

2. Polymerization Process:
Initiation: Free radicals can be generated using heat, light, or chemical initiators. These radicals react
with MMA to form a new radical.
Propagation: The newly formed radical reacts with other MMA molecules, creating a chain reaction that
leads to the formation of PMMA.
Termination: The reaction can be terminated when two radicals combine, or by chain transfer
reactions, leading to various molecular weights and structures.

3. Physical Properties
Amorphous Nature: PMMA is an amorphous polymer, meaning it does not have a crystalline
structure. This contributes to its clarity and transparency.
Thermal Properties: PMMA has a glass transition temperature (Tg) around 100°C (212°F), above
which it becomes more rubbery and less rigid.
Mechanical Properties: It has good tensile strength and impact resistance, though it is more brittle
than some other plastics.

4. Applications Based on Properties

Optical Clarity: Its high light transmittance makes PMMA suitable for applications such as lenses,
screens and lighting fixtures.
Durability: Its weather resistance allows it to be used in outdoor applications like signs and displays.
Biocompatibility: In medical applications, PMMA is used for implants and prosthetics due to its
compatibility with biological tissues.

5. Environmental and Sustainability Considerations

Recycling: PMMA can be recycled, though it is less common than other plastics. The recycling process
can involve mechanical recycling or chemical De-polymerization.
Degradation: While PMMA is durable, it does not biodegrade easily and can contribute to
environmental plastic pollution.

 Synthesis Procedure
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Preparation
Ensure all glassware is clean and dry.
Purge the reaction flask with an inert gas (nitrogen or argon) to remove oxygen, which can interfere
with the polymerization process.

Weighing and Mixing

Weigh the appropriate amount of MMA and, if using, the solvent.
Add the MMA (and solvent, if applicable) to the reaction flask.

Adding the Initiator

Weigh and add the initiator to the flask. The amount will depend on the desired molecular weight
and degree of polymerization.

Heating
Heat the mixture to the initiator’s decomposition temperature (typically around 60-80°C for
AIBN).
Stir the mixture continuously to ensure uniform heating and mixing.

Polymerization Reaction
Maintain the reaction temperature for a specific time (usually several hours), depending on the
desired molecular weight and conversion rate.
Monitor the temperature throughout the reaction.

Termination
Once the desired conversion is reached, the reaction can be terminated by cooling the flask or
adding a chain terminator (such as methanol) if necessary.

Cooling and Precipitation (if applicable)

Allow the mixture to cool. If a solvent was used, PMMA can be precipitated by adding the reaction
mixture to a non-solvent (e.g., water or ethanol).
Collect the precipitated PMMA by filtration.

Purification
Wash the collected PMMA with a non-solvent to remove unreacted monomers and initiators.
Dry the PMMA in a vacuum oven at a low temperature to remove any residual solvent.

Characterization
Characterize the synthesized PMMA using techniques such as gel permeation chromatography
(GPC) for molecular weight, infrared spectroscopy (FTIR) for functional group analysis, and
differential scanning calorimetry (DSC) for thermal properties.

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❖ OBSERVATION:

1. Weight of empty watch glass (W1) = 23.161 g.

2. Weight of watch glass + polymer formed (W2) = 40.467 g.
3. Weight of polymer formed (W2 – W1) = 17.306 g.

❖ CALCULATION:

1. M.W. of MMA = 100.114g/mol

2. M.W. of hydrogen peroxide (H₂O₂) = 34.026g/mol
3. Moles of MMA= 0.0999mol
4. Moles of H₂O₂= 0.0147mol
5. A/F Mole Ratio = 6.8
6. Weight of MMA = 50.06g.
7. Weight of H₂O₂ = 10.21g.
8. Moles of MMA = (Weight of MMA (g) / M.W. of MMA (g/mol))
= 0.1998mol
9. Moles of H₂O₂ = (Weight of H₂O₂ (g) / M.W. of H₂O₂)
= 0.2946mol

RESULT: Weight of PMMA =0.1998mol×100,120g/mol×0.90=18,002.5g

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PROPERTIES:

PROPERTY NAME PROPERTY VALUE

THERMAL PROPERTIES Glass transition 105 - 110°C.

temperature
Thermal conductivity 0.19 - 0.30 W/m·K.

Specific heat capacity 1.3 - 1.5 J/g·K

Thermal stability Good

MACHENICAL Young’s modulus 2.0 to 3.0 GPa
PROPERTIES
Yeild strength 50 MPa to 70 MPa

Tensile strength 60 MPa to 90 MPa

Compressive strength 90 MPa to 130 MPa

ELECTRICAL Electrical resistivity 10¹³ to 10¹⁶ Ω·cm

PROPERTIES
Dielectric constant 2.6 to 3.4

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 PROPERTIES:

PROPERTY NAME PROPERTY VALUE

GENEREL PROPERTIES Molecular Formula (C₅H₈O₂)ₙ

Synonyms
Acrylic Glass

Structure
2D

3D

COMPUTED Density 1.17 to 1.20 g/cm³

PROPERTIES
Boiling Point 270°C to 350°C

Flash Point 330°C to 350°C

Molecular Weight 100,000 to 1,000,000 g/mol

Compressive strength 70 MPa to 110 MPa

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 Applications:
Acrylic Glass: Commonly used in place of glass in applications like windows, skylights,
and aquariums.
Automotive: Used in headlights and taillights due to its clarity and impact resistance.
Medical Devices: Utilized in various medical applications, including dental prosthetics and
intraocular lenses.
Signage and Displays: Often used for illuminated signs and display cases

 Safety and Hazard Information:

Poly-methyl methacrylate (PMMA) is generally considered safe for various applications, but there
are important safety considerations to keep in mind:
1. Physical Hazards
Fire Hazard: PMMA is flammable and can ignite under high heat or flame. It's important
to store and use it away from open flames and sources of ignition.
Dust: Grinding or cutting PMMA can produce dust that may be a respiratory irritant. Proper
ventilation and personal protective equipment (PPE) like masks should be used during
processing.
2. Chemical Hazards
Monomer Exposure: During the production of PMMA, exposure to methyl methacrylate
(MMA), the monomer used to produce PMMA, can occur. MMA is toxic and can cause
irritation to the skin, eyes, and respiratory system. Adequate ventilation and protective gear
are necessary when handling MMA.
Solvent Interaction: PMMA can be affected by certain solvents (e.g., acetone, ethanol),
leading to degradation or cloudiness. Avoid using incompatible solvents for cleaning or
handling.
3. Health Effects
Skin Contact: Prolonged contact with MMA can cause skin irritation and sensitization.
Inhalation: Inhalation of vapors from MMA or dust from PMMA processing can lead to
respiratory issues. Symptoms may include coughing, shortness of breath, or throat
irritation.
Eye Contact: MMA can cause irritation to the eyes. If exposure occurs, rinse immediately
with plenty of water and seek medical attention.
4. Environmental Impact
PMMA is not biodegradable and can contribute to plastic pollution if not disposed of
properly. Recycling options exist, but facilities may be limited depending on location.
Recommendations
PPE: Use gloves, goggles, and respirators when handling MMA or PMMA in powder form.
Ventilation: Ensure adequate ventilation in areas where PMMA is processed or used.
 Emergency Procedures: Have safety data sheets (SDS) available and train
staff on proper handling procedures and emergency responses for chemical
exposure

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 Reference:

1. Polymethylmethacrylate (PMMA, Acrylic) Archived 2015-04-02 at the Wayback Machine.

Makeitfrom.com. Retrieved 2015-03-23.
2. ^ Wapler, M. C.; Leupold, J.; Dragonu, I.; von Elverfeldt, D.; Zaitsev, M.; Wallrabe, U.
(2014). "Magnetic properties of materials for MR engineering, micro-MR and
beyond". JMR. 242 (2014): 233–
242. arXiv:1403.4760. Bibcode:2014JMagR.242..233W. doi:10.1016/j.jmr.2014.02.005.
PMID 24705364. S2CID 11545416.
3. ^ Jump up to:a b Refractive index and related constants – Poly(methyl methacrylate)
(PMMA, Acrylic glass) Archived 2014-11-06 at the Wayback Machine.
Refractiveindex.info. Retrieved 2014-10-27.
4. ^ Plexiglas history by Evonik (in German).
5. ^ "DPMAregister | Marken - Registerauskunft". register.dpma.de. Retrieved 2021-09-29.
6. ^ Congressional Record: Proceedings and Debates of the 77th Congress First
Session (Volume 87, Part 11 ed.). Washington, D.C.: U.S. Government Printing Office.
1941. pp. A2300–A2302. Retrieved 3 August 2020.
7. ^ "Polymethyl methacrylate | chemical compound". Archived from the original on 2017-10-
31. Retrieved 2017-05-22.
8. ^ "polymethyl methacrylate", Dorland's Illustrated Medical Dictionary, Elsevier
9. ^ "polymethyl methacrylate". Merriam-Webster.com Dictionary. Merriam-Webster.
10.^ David K. Platt (1 January 2003). Engineering and High Performance Plastics Market
Report: A Rapra Market Report. Smithers Rapra. p. 170. ISBN 978-1-85957-380-
8. Archived from the original on 21 April 2016.

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