Project Report

Polymethyl methacrylate (PMMA) and

its uses

CL623 - Polymer Science and Technology

1st May 2019

Shubham Kumar
150107056
1. Introduction
Polymethyl methacrylate (PMMA), commonly referred as acrylic or acrylic glass is a rigid and
transparent thermoplastic used as substitute of glasses with added advantage of being
shatterproof. PMMA also traces their widespread application in inks, coatings and in medical
technologies. It provides enhanced optical clarity and transmissivity. It incurs less damage to
the tissues when shattered. PMMA is used as a cost-effective alternative for Polycarbonates
(PC), where high strength is not required. However, blends can be made to upgrade the strength
and still retain the optical characteristics. Acrylic acid was first synthesised in 1843,

Fig. 1 Structure of (i) MMA and (ii) PMMA

subsequently Methacrylate was prepared from acrylic acid (1865). Methanol upon reaction
with methacrylic acid gives methyl methacrylate (MMA). Fittig and Paul (1877), two German
chemists were first one to discover the methodology of synthesising PMMA from MMA. Later
Otto Rohm (1936) patented the product under brand name “Plexiglas” and made it
commercially available. WWII has witnessed extensive use of PMMA in their war crafts, such
as periscopes of submarines, wind-shields of airplanes etc. In the subsequent sections we will
discuss about the properties and preparation methodology in further detail.

2. Synthesis:
Owing to the extensive use of PMMA, significant research work has been done in this field.
Various methods of polymerization can be employed to synthesise PMMA. Most frequent one
is the free radical polymerization of Methyl methacrylate. Methods of polymerization is
broadly classified as homogeneous and heterogeneous, homogeneous involves bulk or solution
polymerization and heterogeneous is comprised of emulsion or suspension polymerization.
Radical generation can be facilitated by heat, radiation or chemical agents. Heat provides a
spontaneous pathway for polymerization, but being extremely slow it is of no industrial use.
The predominant mechanism used for preparation on industrial scale is by free radical
mechanism [1,2].

Fig. 2 Steps involved in synthesis of PMMA

2.1. Polymerization initiated by radiation: Light or-radiation is capable of initiating the

polymerization reaction. Use of sensitizers is not required when photoinitiation of MMA
is done using visible or ultraviolet light. Although, it is still unclear that photoinduced
polymerization involves excited state mechanism or free radical mechanism [3]. Usually,
sensitizers (photochemically active compounds) are added. Common examples are
benzoyl peroxide, anthracene, t-butyl peroxide and azoisopropane etc.
Photopolymerization is among the best available techniques to produce polymers with
cross linking properties and well defined behaviour.

Fig. 3 Photoinitiation Mechanism for Benzophenone [4]

2.2 Thermally initiated polymerization: 2,2’-azobisisobutyronitrile (AIBN) is most
frequently used thermal initiator for polymerization of PMMA. They form free radicals upon
heating, which in turn triggers the polymerization. Free radical polymerization is capable of
producing polymers with low conversion and high molecular weight. Combination and
disproportionation as well as termination by combination are the mechanism through which
polymerization terminates. Head to head combination results in doubling the molecular
weight of polymer and terminating the chain.

Fig. 4 Thermal initiation of AIBN

2.2 Suspension polymerization: This method is employed to produce small beads of

PMMA. Monomer is blend with dispersants and water of larger volume and suspension of
monomer is prepared. To stabilize the process dispersants are used, for instance PVC, gelatin,
and derivatives of cellulose are used as dispersants. To control the size of beads, dispersants
and stirring conditions are adjusted. Aqueous phase facilitates the removal of heat and helps
in enhancing the rate of polymerization [5]. Beads of polymer can easily be separated after
completion by filtration and is dried thereafter.

2.3 Emulsion polymerization: It is used to dispersions of PMMA. Polymerization via free

radical mechanism of monomers occurs in colloidal suspension. Usually, to form micelles
surfactants are added. Water soluble initiators (like Potassium persulfate) are used to generate
free radicals. Monomers tend to migrate to micelles and the concentration increases which
facilitates the polymerization. It produces polymers of higher molecular weights and yields
higher rate of conversion inside the micelles. The PMMA particles created by this mechanism

Fig. 5 schematic of emulsion polymerization [169]

are of smaller size (i.e. in range of 0.1µm). It is used to produce paper processing and coating
agents, paints and textile additives.

Properties of PMMA
PMMA is a linear polymer, which is amorphous in nature and is best used for its rigidity and
hardness. It offers weathering resistance and the transparent nature fetches its application in
optical devises. Its molecular mass varies based on the method of polymerization adopted.
Important properties and its values are tabulated below.

Property Value
Specific gravity 1.18
Melting temperature 160˚C
Tensile strength 65 MPa
Flexural strength 90 MPa
Refractive index 1.4914

It surpasses both polystyrene and glass in terms of impact strength, however it still lags
behind polycarbonate and other polymers. PMMA catches fire at 460˚ C and produces water,
carbon monoxide and carbon dioxide as well as certain organic compounds having lower
molecular weight like formaldehyde. PMMA is soluble in many organic solvents and is also
resistive towards other chemicals due to presence of ester groups.

PMMA is modified according its use case by adding different comonomers and fillers, as
pure form does not serve specific purposes. Some of the examples are stated here.
To improve the impact strength comonomers butyl acrylate is added and methacrylic acid is
added to enhance the transition temperature for being used at extreme thermal conditions.
Dyes are added to improve the aesthetics and makes them useful for decorative applications.
To improve cost effectiveness fillers are used whereas to improve processing properties and
impact resistance plasticizers are added. Small proportions of acrylate are used in PMMA to
improve the heat processing qualities and makes the polymer resistive to unzipping.

Acrylics have an added advantage for their use is that they do not release BPA (Bisphenol A)
when brought in contact with water. Whereas, other substitutes like Polycarbonate releases
BPA upon hydrolysis.
Applications of PMMA
PMMA finds profound application due to its inherent physical and chemical properties.
Transparency and resistance to scratches and tearing makes it a substitute for glasses and
polycarbonates wherever high resistance to impact is not of utter importance. In this section
we would present the diverse application of PMMA.

Transparent glass substitutes: PMMA is predominantly used in construction of aquariums

and designer glasses for buildings. Viewing ports
of submarines and other submersible devices
which operates at higher pressures are made of
PMMA. Lenses in exterior lights of automobiles
as well as in the lighthouses are primarily PMMA
based. Historically, window panes of war ships,
aircrafts and gears of soldiers were used as an
improvement over glasses as it does not tear the
tissues of skin and incurs less damage to the user. Fig. 5 Panels of aquarium made of PMMA
Precisely cut panels of acrylic is used in the “light
pipe”, it significantly improves the attenuation ratio over glasses.

Implants and medical technologies: PMMA inherits a special property of being highly
compatible with human tissues. Upon surgery of
cataracts the synthetic intraocular lenses which are
implanted is made up of PMMA. In orthopaedic
surgeries, remodelling of lost bones and implant is done
using PMMA bone cement. Even though PMMA is
biologically compatible with human tissues, MMA is
considered as a potential irritant. In cosmetic surgeries,
to reduce wrinkles and scars, suspension of PMMA
comprised of microspheres is injected under skin as a
soft tissue filler. Conventional treatment (Plombage) of Fig. 6 Intraocular lens ( PMMA)
tuberculosis involved filling of pleural space in lungs with balls made up of PMMA to
compress the infected portions of lung.
Applications in dentistry: As the biocompatible nature
of the polymer is mentioned, it is proactively being used
in modern dentistry applications, particularly in
fabrication of artificial teeth, prosthetics and other
orthodontic applications. Pre polymerized PMMA powder
(spheres) upon mixing with MMA in presence of Benzoyl
peroxide as initiator and suitable accelerator yields solid
PMMA structure. Mechanical properties along with
aesthetic nature of PMMA makes it unparalleled candidate
for construction of dental prosthetics. Fig. 7 Use of PMMA in bone implant

Aesthetic and artistic uses: Acrylic paint primarily consists of suspension of PMMA in water,
however hydrophobic nature of PMMA and needs to
be facilitated by a group which inherits both nature.
Modern practices in furniture making from 1960
onwards involved use of Lucite and other PMMA
products. It is also used in manufacturing of laser
discs and also as backlights in TFT-LCDs.
Fig. 8 Lexus car sculpture

References:
[1] Stickler, M.; Rhein, T., “Polymethacrylates” in Ullmann’s Encyclopedia of Industrial
Chemistry, 5th ed., Elvers, B.; Hawkins, S.; Schultz, G. Eds., VHS: New York, 1992, A21, 473.

[2] Kine, B.B; Novak, R.W., “Acrylic and Methacrylic Ester Polymers” in Encyclopedia of
Polymer Science and Engineering, Wiley: New York, 1985, 262.

[3] Gruber, H.F., Prog. Polym. Sci., 1992, 17, 953.

[4] McGrath, J. E.; Wilkes, G.L.; Ward, T., ibid.

[5] Stickler, M.; Rhein, T., Op. Cit.