Apr. 14, 2025
What is MMA monomer? Methyl methacrylate (MMA) is a monomer that’s also known as methacrylic acid, methyl ester.
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A key building block for acrylic-based polymers, MMA has applications that include safety glazing, exterior paints, vinyl impact modifiers, adhesives, illuminated light displays, and more. There are several synthetic ways to make the MMA chemical as the one most widely used is the three-step process of adding acetone to hydrogen cyanide (HCN) and moves to acetone cyanohydrin.
The history of the formulation of methyl methacrylate monomer began during a time when acrylic acids were first being synthesized in the early s. German chemists took roughly 85 years to develop acrylic acid in . Then it took another 22 years for them to make methacrylic acid, and then from that step methanol was added to form the chemical reaction of methyl methacrylate, which would become known as acrylic polymer.
Yet still in that time, the possibilities of using methacrylic acid to make was still not readily understood. It wasn't until roughly the s when acrylic polymers appeared with the polymerization of metal acrylate.
In this article, we provide a general overview of this important monomer, covering everything from its polymerization to important safety and handling considerations. Here are 5 key facts about methyl methacrylate monomer (MMA):
As previously mentioned, MMA is foundational for many acrylate polymers and is an essential comonomer in paint, coatings, and adhesives resin formulations. A comonomer consists of one monomer that is added to another monomer to become a copolymer. In free radical initiated copolymers, MMA chemical structure elevates the Tg (glass transition) and contributes durability, strength, transparency, and UV and abrasion resistance.
The chemical structure of MMA is shown below.
Here are several other key pieces of information about methyl methacrylate:
CAS Number
80-62-6
EINECS Number
201-297-1
Empirical Formula
C5H8O2
Molecular Weight
100.12
Melting Point
-48 °C (-54℉)
Boiling Point
101°C (214℉)
Flash Point
2°C (36℉)
Additionally, it’s important to note that the Tg value for PMMA homopolymer is 105°C. In polymers, MMA contributes durability, hardness, impact strength, scratch resistance, and clarity.
Polymerization involves bonding smaller monomers so that they become a polymer. When it comes to polymerization, the range of acrylic copolymers that can be used with MMA is extensive. Monomer feeds can include:
The monomer composition selected for copolymers is driven by the desired Tg of the resin, ranging from -30˚C to > 30˚C. The free-radical reactivity ratios for MMA copolymer systems have been well studied and are available in the literature.
For reference Tg values of some comonomers, please consult the table below.
AA
Sty.
MMA
BA
2-EHA
87˚C
100˚C
105˚C
-45˚C
-55˚C
Methyl methacrylate monomer readily polymerizes to form high molecular weight homopolymers (where a polymer is created from many copies of a single monomer) and copolymers.
The principal use for MMA monomer is to form polymethyl methacrylate (PMMA) homopolymer for the production of cast and extruded acrylic sheets. These cast PMMA sheeting products exhibit good optical clarity, high transparency, and UV stability. Methyl methacrylate MMA products and applications include…
Outside of glazing and sheet applications, the largest use for MMA is as a comonomer in paints and coatings, such as exterior paints and paper coatings. Polymers and copolymers of methyl methacrylate are in:
These polymers are produced as waterborne, solvent, and dispersion resins for these applications. Methyl methacrylate-butadiene-styrene (MBS) resins are used as impact modifiers for clear, rigid PVC, an example of which would be bottles. In addition, MMA can partially replace styrene monomer in unsaturated polyester resins to give better weather resistance and longer outdoor life.
For products such as signage, displays, bath enclosures, spas and tabletop surfaces, as well as automotive lights and light fixtures, methyl methacrylate polymerization can be cast into a solid form.
Applications also include engineering adhesives. These are liquid, reactive, durable adhesives for bonding a variety of substrates, and they consist of MMA monomer with PMMA. Low-viscosity, rapidly curing MMA reactive resin systems are highly effective for sealing and filling cracks and pores in concrete surfaces and structures.
These adhesives are desired due to their ability to bond differing surfaces together, the high resistance of fatigue, and a higher peel rate. MMA adhesive can cure at room temperature while being more temperature resistant.
Other MMA copolymer applications include mining flocculants, soil stabilization polymers, waterproofing agents, and oil field drilling fluids. While MMA can cause safety concerns when coming in direct contact with the skin and eyes, and cause serious problems with the nose, through and lungs, PMMA is compatible with human tissue. It is used in several medical technologis such as acrylic bone cement and implant introcular lenses for the eyes.
MMA was once commonly used for nail enhancements. However, FDA research concluded that it was poisonous and should not be used in this manner. While some state have banned MMA nails, other states have not made it illegal as it can still be found in some nail salons.
To provide an example of a methyl methacrylate application, we’ve included an example of an emulsion composition involving MMA.
Below is a typical paint formulation using MMA monomer in a copolymer.
Deionized water
90.9 g
Tg (Measured value)
-12˚C
Viscosity
99 mPa.s
Nonvolatile substance, ca
0.50%
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Acid value
7.2 mg KOH/g
Particle size
0.22 μm
pH
9.0 (Ammonia)
Giving proper attention to safety is critical when handling methyl methacrylate for several reasons.
MMA is a flammable, colorless liquid which melts at -48˚C and boils at 101˚C. While MMA is soluble in the most organic solvents, it is insoluble in water.
In addition to being flammable, direct contact with MMA can cause irritation of the eyes, skin, nose, and throat. Considered a skin sensitizer, methyl methacrylate can produce allergic reactions from contact, in which future exposures can cause itching and a skin rash.
Even more seriously, inhalation of MMA vapor or mist can cause irritation of the nose, throat, and lungs and can be fatal in high concentrations.
Because MMA can violently homo-polymerize and can generate considerable heat and pressure, MMA is only provided in a stabilized form. To ensure MMA’s stabilizer can function effectively, it’s important to store MMA under air and replenish the dissolved oxygen.
To obtain a Safety Data Sheet (SDS) and other handling information on MMA, please contact us or call us. At Gantrade Corporation, we encourage our customers to have a comprehensive understanding of the health, safety, environmental, and regulatory information on our products before handling.
If you’re looking to purchase high-purity MMA, Gantrade Corporation provides this monomer in 20 MT (44,080 lb.) for industrial use only.
The purity of our methyl methacrylate is ≥ 99.9%, and our MMA contains only traces of water (0.035% max.) and acidity as methacrylic acid (0.% max.).
For storage and transportation, we’ve added an inhibitor, usually 15-18 ppm of Topanol A, which is FDA compliant and nonstaining and exhibits low volatility.
If you have questions about substituting Topanol for MEHQ or commingling Topanol-stabilized MMA with MEHQ-stabilized MMA, simply contact us, and we’d be happy to answer your questions.
Below is a table containing Gantrade’s specifications for methyl methacrylate.
Item
Specifications
Appearance at 25 °C
Clear, colorless liquid
Purity by GC, %
≥ 99.9
Color, Pt-Co
≤ 5
Moisture weight % by K.F.
≤0.02
Inhibitor Concentration,
ppm Topanol A
15-18
Acidity, %
≤0.
There are many uses for MMA monomers in common commercial, industrial, and residential uses. Manufacturers can take advantage of obtaining high purity MMA from our company that will fit into their production processes and products.
Acrylate esters in general, which include butyl acrylate (BA), 2-ethylhexylacrylate (2-EHA), methyl methacrylate (MMA), butyl methacrylate (BMA), and others, represent a versatile family of building blocks for thousands of copolymer compositions. Acrylic resins based on these monomers exhibit excellent weather resistance, high gloss and color retention, and durability. For these reasons, they are the preferred compositions for architectural and industrial coatings, automotive finishes and a wide variety of other applications.
Acrylic ester copolymerization is an important technique to achieve systematic tailoring of properties required in a broad range of end-use applications. Glacial acrylic acid (GAA) and glacial methacrylic acid (GMMA) are acrylate monomers used to functionalize acrylic copolymers.
The short-chain acrylic monomers like methyl methacrylate and other monomers like styrene produce harder, more brittle polymers, with high cohesion and strength characteristics. The long-chain monomers like butyl acrylate and 2-ethylhexylacrylate enable soft, flexible, tacky polymers with lower strength characteristics. Monomers like ethyl acrylate, butyl methacrylate, and vinyl acetate contribute more intermediate glass transition and hardness values. Co-monomers such as acrylonitrile and (meth)acrylamide, can improve solvent and oil resistance.
By managing the comonomer ratios and the glass transition temperatures, chemists can balance hardness and softness, tackiness and block resistance, adhesive and cohesive properties, low-temperature flexibility, strength and durability, and other key properties to facilitate end-use goals.
Advancements in film mechanical properties; chemical, water, and abrasion resistance; durability; adhesive properties; and solvent resistance have driven the growth of acrylic copolymers, especially in water-borne technologies. A major contributor to these performance enhancements has been new polymer crosslinking chemistries. Exemplary of this trend is the use of diacetone acrylamide functional monomer, which can be incorporated in acrylic systems to afford controlled crosslinkability.
Let’s take a look at some key facts on acrylate monomers used in CASE applications.
Acrylic-based coatings and adhesives can be classified into all-acrylic formulations in which the building blocks are exclusively acrylic and methacrylic ester types; acrylic-styrene formulations, which also contain styrene; and vinyl-acrylic formulations which also contain vinyl acetate monomer (VAM). The various monomers used in the copolymers can differ widely in glass transition temperature (Tg); the copolymer hydrophobic-hydrophilic balance; hardness and flexibility; and weathering/sunlight resistance. Even with a fixed Tg, copolymers with different monomer combinations vary significantly in the properties of the final paint and coatings. The most common formulations are copolymers of MMA, BA, 2-EHA and GAA, and also VAM in vinyl acrylic polymers.
Glacial acrylic acid monomer (GAA) and glacial methacrylic acid (GMMA) are unsaturated carboxylic acid co-monomers used to produced acid functional and crosslinked acrylic copolymers and polyacrylic acids. GAA and GMMA readily copolymerize with acrylic and methacrylic esters, ethylene, vinyl acetate, styrene, butadiene, acrylonitrile, maleic esters, vinyl chloride, and vinylidene chloride. Copolymers which contain GAA or GMMA can be solubilized or exhibit improved dispersions in water; the carboxylic acid moiety can be used for coupling or crosslinking reactions, and improved adhesion. Chemists use GAA and GMMA copolymers in the form of their free acid, ammonium salts or alkali salts. Copolymerization accounts for approximately 45 percent of the consumption of acid monomer (the manufacture of acrylate esters is the other major use).
Acrylic copolymer formulations often contain four or more different monomers. We can estimate the glass transition temperature of a random copolymer by using the weight fraction of the different monomers and their Tg values for the homopolymer. This method assumes that the repeat unit of the copolymer can be divided into weighted additive contributions to the Tg that are independent of their neighbors. Reference Tg values for several key monomers are shown below.
Glass transition temperatures, Tg (◦C), of various monomers used in acrylic copolymers:
Monomer Tg (◦C) MMA 105 Styrene 100 Butyl Methacrylate 20 Vinyl Acetate Monomer 30 Glacial Methacrylic Acid 228 Glacial Acrylic Acid 87 Butyl Acrylate -45 2-Ethylhexyl Acrylate -65Advanced Crosslinking Technology
Crosslinking chemistry based on diacetone acrylamide (DAAM) and adipic acid dihydrazide (ADH), known as keto-hydrazide crosslinking, represents the most advanced technology for controlled crosslinking of acrylic latex polymers. It involves the direct reaction of the pendant ketone moiety on the DAAM segment with the hydrazide moiety of the ADH.
Self-crosslinking chemistry between diacetone acrylamide and adipic acid dihydrazide begins with copolymerizing DAAM into an acrylic copolymer, using DAAM concentration at ~1-5 wt. % of the monomer mixture. This makes the emulsion copolymer crosslinkable via a pendant ketone carbonyl moiety. Afterwards, the following steps will complete the process:
See Gantrade’s article on technology of DAAM and ADH crosslinking in acrylic polymers.
Primary applications that take advantage of the characteristics afforded by acrylic copolymers include multiple adhesives, especially pressure-sensitive adhesives(PSA); paint & coatings; caulks & sealants; textile & paper finishes; and printing inks. Because acrylic monomers contribute clarity, toughness, light & weather resistance, and chemical & moisture resistance, manufacturers use acrylic copolymers in interior, exterior, basecoat, and topcoat paint & coating formulations. Paint & coatings, adhesives & sealants, cast & extruded sheet and glazing, and printing inks are among the largest and highest growth global applications for acrylic and methacrylic ester monomers.
Processors use hydroxyfunctional (HEA, HEMA) and carboxyfunctional (GAA, GMAA) acrylic systems in applications like powder coatings were crosslinking is accomplished through isocyanates or melamine crosslinking agents.
In addition to being flammable, direct contact with acrylic monomers can cause irritation of the eyes, skin, nose and throat, and are often considered to be skin sensitizers.
Acrylates monomers will readily self-polymerize if not properly inhibited, stored, and handled. Polymerization can be rapid and violent, generating large amounts of heat and pressure. An intercompany committee prepared an excellent reference guide to essential information on the safe handling and storage of inhibited (usually MEHQ) acrylic monomers. In order for the inhibitor to function effectively, it is important to store stabilized acrylate monomers under air and to replenish dissolved oxygen over time. See this brochure for more information: http://www2.basf.us/acrylicmonomers/pdfs/AE_Brochure_3rd.pdf
Glacial acrylic acid requires special attention. The freezing point of GAA is 13°C (55°F); storage temperatures should be maintained at 15 to 25°C (59 to 77°F) at all times. Users should avoid Freezing (or partial freezing) of GAA, because the crystallized GAA excludes the MEHQ and the solid GAA will contain a deficiency of inhibitor and oxygen. The temperature of the medium used to thaw acrylic acid should never be greater than 35-45°C (95-113°F). During thawing, processors should mix the GAA to redistribute the inhibitor and resupply dissolved oxygen. Further, GAA slowly dimerizes upon standing to form diacrylic acid. While this dimer-forming reaction has a slow rate and is not hazardous, diacrylic acid can affect the performance of the GAA at high concentrations by interfering with the free radical polymerization process.
At Gantrade, we encourage our customers to have a comprehensive understanding of the EH&S information and safe product handling procedures when working with acrylate monomers.
If you’re looking to purchase high-purity acrylate acid and ester monomers, Gantrade Corporation provides butyl acrylate, 2-ethylethyl acrylate, methyl methacrylate, glacial methacrylic acid, butyl methacrylate, and other specialty acrylic monomers for industrial use. Our packaging sizes can be 20 MT (44,080 lbs.) tank trucks, rail cars and drums, depending on the specific monomer and location.
Contact us to discuss your requirements of additives for polymers. Our experienced sales team can help you identify the options that best suit your needs.
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