| HS Code | |
| Product Name | Methyl Methacrylate |
| Iupac Name | Methyl 2-methylprop-2-enoate |
| Cas Number | 80-62-6 |
| Ec Number | 201-297-1 |
| Un Number | 1247 |
| Molecular Formula | C5H8O2 |
| Molecular Weight | 100.12 g/mol |
| Appearance | Colorless liquid |
| Odor | Pungent, fruity, acrid odor |
| Boiling Point | 100.3 °C (212.5 °F) |
| Melting Point | -48 °C (-54.4 °F) |
| Density | 0.943 g/cm³ at 20 °C |
| Vapor Pressure | 38 mmHg at 25 °C |
| Vapor Density | 3.45 (air = 1) |
| Flash Point | 10 °C (50 °F) closed cup |
| Autoignition Temperature | 421 °C (790 °F) |
| Solubility In Water | Slightly soluble; 15 g/L at 20 °C |
| Refractive Index | 1.414 at 20 °C |
| Viscosity | 0.6 mPa·s at 20 °C |
| Log P | 1.38 |
| Polymerization | Readily polymerizes; typically inhibited with hydroquinone monomethyl ether |
As an accredited Methyl Methacrylate factory, we enforce strict quality protocols—every batch undergoes rigorous testing to ensure consistent efficacy and safety standards.
| Packing | Methyl Methacrylate is packaged in 200 L steel drums, sealed and labeled flammable, stored cool, away from ignition sources. |
| Container Loading (20′ FCL) | Methyl Methacrylate, UN 1247, Class 3 flammable liquid, stabilized, properly loaded in 20′ FCL under IMDG rules with secure stowage. |
| Shipping | Methyl methacrylate, stabilized, is shipped as UN 1247, Class 3 flammable liquid, Packing Group II. Use approved UN packaging with polymerization inhibitor; keep cool, away from heat, sparks, and oxidizers. Mark/placard as flammable. Follow applicable ADR, IMDG, IATA, and DOT regulations. |
| Storage | Store methyl methacrylate in a cool, dry, well-ventilated, flammable-liquid area away from heat, sparks, open flames, and direct sunlight. Keep containers tightly closed, upright, labeled, and inhibited. Store below 30°C, preferably at 25°C. Avoid oxidizers, peroxides, initiators, acids, bases, and food. Maintain inhibitor and dissolved oxygen; do not inert-blanket. Use grounded, explosion-proof equipment. Protect from static discharge and impact. |
| Shelf Life | Stabilized methyl methacrylate typically has a 6–12 month shelf life when stored cool, dark, sealed, and away from heat, light, and initiators. |
Continuous cell casting lines processing methyl methacrylate monomer at thicknesses above 18 mm require internal heat-transfer management that accounts for the monomer’s polymerisation enthalpy of approximately 57 kJ mol−1 and a boiling point of 100.3 °C. The monomer charge for cast PMMA is specified at ≥99.8 wt% purity, with water held below 0.05 wt% and 4-methoxyphenol inhibitor typically maintained at 5–15 ppm to prevent premature polymerisation during storage. A production-scale formulation addition ratio for cell casting uses methyl methacrylate as the 100-part monomer base, azobisisobutyronitrile or lauroyl peroxide initiator at 0.02–0.08 phr, n-dodecyl mercaptan chain transfer agent at 0.05–0.20 phr, and UV absorber packages at 0.05–0.25 phr depending on outdoor exposure class. The downstream manufacturing sequence begins with a prepolymer syrup polymerised to 8–12% conversion and adjusted to a viscosity of 0.6–1.5 Pa·s at 25 °C, followed by vacuum deaeration and pouring into glass cell moulds sealed with flexible gaskets. The filled cells enter a water bath ramped from 60 °C to 80 °C; after gelation the sheets are transferred to a forced-air post-cure oven at 120–130 °C for 4–8 h. The controlling failure mode on thick-section lines is boiling of the monomer inside the cell when exotherm removal is insufficient, producing trapped vapour voids and visible optical haze. Residual MMA is therefore driven below 0.4 wt% for low-odour, high-toughness sheet intended for food-contact or optical applications. Compliance boundaries include ISO 7823-1:2003 for cast PMMA sheet classification, ASTM D4802-16 for weathering and optical properties, and FDA 21 CFR 177.1010 for semirigid acrylic polymers in food-contact articles. Terminal finished product types produced from this processing route include monolithic cell-cast sheet for aquarium glazing, illuminated signage, light guide plates, aircraft transparencies where heat-distortion resistance is critical, and external architectural screens requiring ultraviolet stabilisation.
In solvent-borne acrylic polyols formulated for automotive OEM and refinish topcoats, methyl methacrylate is charged into free-radical solution polymerisation at 18–28 wt% of total resin solids, with butyl acrylate and 2-hydroxyethyl methacrylate forming the balance. The monomer feed ratio directly controls crosslinked-network hardness and resistance to high-shear polishing after film cure; raising MMA beyond approximately 30 wt% increases resin glass transition temperature and high-solid viscosity to a level that requires additional ketone or ester solvent, conflicting with 2004/42/EC VOC ceilings for automotive refinishing. The polymerisation line is typically a 6,000–10,000 L 316L stainless steel reactor fitted with a turbine agitator operating at 120–150 rpm, a monomer feed dosing system for 5–8 h addition, and an initiator dose of di-tert-amyl peroxide at 1.5–3.0 wt% on total monomer. Reaction temperature is held at 120–140 °C in butyl acetate or xylene at 60–70 wt% solids, with chain transfer agents used to maintain molecular weight between 3,000 g/mol and 8,000 g/mol and polydispersity near 1.8–2.4. After packaging, the acrylic polyol is crosslinked with 1,6-hexamethylene diisocyanate trimer at an NCO:OH index of 1.05–1.15; coating lines monitor König pendulum hardness according to ISO 1522:2006, VOC by ASTM D2369-20 or ISO 11890-2:2020, and solvent resistance by ASTM D5402-19 methyl ethyl ketone double rubs. The terminal finished product matrix includes high-solids clearcoats, pigmented basecoats for plastic automotive trim, and fast-cure refinish topcoats where the MMA hard segment supplies the scratch resistance demanded by automated car-wash exposure.
Seeded semibatch emulsion polymerisation of all-acrylic and styrene-acrylic dispersions introduces methyl methacrylate into the pre-emulsion at 25–35 wt% of total monomer as the hard-segment modifier. The manufacturing line consists of a jacketed glass-lined reactor with an anchor agitator, a static mixer used to prepare the monomer pre-emulsion, and separate feeds for an ammonium persulfate initiator at 0.3–0.7 wt% on monomer and sodium metabisulfite reducing agent at 0.2–0.5 wt%. The monomer feed is delivered under monomer-starved conditions over 3.5–5.0 h at 80 °C ± 2 °C, followed by a post-reaction chaser of tert-butyl hydroperoxide and ascorbic acid to reduce free MMA below 500 ppm in the finished dispersion. The addition ratio for a low-coalescent architectural binder is commonly MMA 25–35 wt%, butyl acrylate 45–55 wt%, methacrylic acid 1.5–3.0 wt%, and phosphate ester surfactant 0.5–1.5 wt% on total monomer. This composition raises the Fox glass transition temperature into the 1–20 °C range and reduces the minimum film formation temperature, thereby limiting coalescent demand under EN 13300 and GB/T 9755 exterior-paint classifications. Volatile organic content is controlled according to ASTM D3960-05 and ISO 11890-2:2020; non-volatile content is verified by DIN EN ISO 3251:2019. The terminal product spectrum includes exterior masonry paints, elastomeric roof coatings, waterborne wood primers, and pressure-sensitive adhesive laminating emulsions where MMA contributes shear resistance and block resistance without requiring solvent-borne coalescents.
| Indicative pre-emulsion monomer split | MMA charge | Butyl acrylate charge | Methacrylic acid charge | Calculated Fox Tg |
|---|---|---|---|---|
| High-tack laminating dispersion | 25 wt% | 70 wt% | 5 wt% | -20 °C |
| Exterior masonry binder | 35 wt% | 62 wt% | 3 wt% | -11 °C |
| Low-coalescent wood primer | 45 wt% | 53 wt% | 2 wt% | 1 °C |
The graft shell of an MBS impact modifier is produced when methyl methacrylate and styrene are graft-polymerised onto a butadiene-styrene rubber latex, with the MMA fraction in the shell charge held at 20–30 wt% of the total core-shell particle. The methyl methacrylate monomer is introduced into an emulsion graft stage in a stirred jacketed reactor at 60–75 °C using a redox initiator system of cumene hydroperoxide and ferrous sulfate-sodium formaldehyde sulfoxylate at 0.1–0.4 wt% on graft monomer. The core latex, typically 50–70 wt% polybutadiene crosslinked with ethylene glycol dimethacrylate at 0.5–2.0 wt%, is charged first, and the MMA-styrene feed is added over 2–4 h to permit controlled grafting at the rubber-water interface. Overgrafting during this stage produces a high free-shell polymer content, which lowers impact efficiency and raises the minimum MBS loading required in the polyvinyl chloride compound. The finished MBS latex is coagulated with calcium chloride or sulfuric acid, washed, dewatered, and spray-dried, yielding a free-flowing powder with a bulk density of 0.25–0.45 g/cm³. In downstream PVC compounding, MBS is added at 3–12 phr on PVC resin in a twin-screw extruder with L/D ratio between 36:1 and 48:1, melt temperature set at 180–195 °C, and screw speed adjusted to avoid shear-induced yellowing. Compliance is assessed by notched Izod impact according to ISO 180:2019 and ASTM D256-10, while electrical and heavy-metal limits for transparent PVC packaging follow RoHS 2011/65/EU. Terminal finished products are transparent rigid PVC sheet, blow-moulded bottles, calendered film, injection-moulded medical components, and packaging where impact strength at refrigeration temperatures and low haze are simultaneous acceptance criteria.
At ambient-to-sub-zero bonding cells for gel-coated composite panels, two-part methyl methacrylate structural adhesives are dispensed through a static mixing nozzle at a 10:1 volume ratio, with the MMA monomer functioning as both reactive diluent and rubber solvent at 40–65 wt% of the resin side. The resin component contains methyl methacrylate, chlorosulfonated polyethylene or nitrile rubber at 15–30 wt%, methacrylic acid adhesion promoter at 2–6 wt%, and an amine stabiliser at 0.5–1.5 wt%; the hardener side carries benzoyl peroxide paste at 2–5 wt% in a plasticiser carrier. The dispenser is a pneumatic cartridge gun with a 24-element static mixing tip, producing working time of 4–15 min at 23 °C and fixture time of 15–25 min on blast-cleaned steel. Surface preparation follows ISO 8501-1 to Sa 2½ for steel and grit blasting or isocyanate primer for aluminium; bond-line gaps from 1 mm to 25 mm are filled without foaming because the MMA system tolerates high wet-film thickness better than cyanate-ester or epoxy paste adhesives. The low-temperature cure window extends to approximately -10 °C, though open time increases below 5 °C and humidity above 80% RH can retard surface cure and leave a tacky film unless an external primer is used. Mechanical acceptance uses ISO 4587:2003 and ASTM D1002-10 lap-shear specimens; production lines also monitor elongation by ISO 527-2:2012 on bonded polyurethane block samples. Terminal finished product types include bus and truck side panels, trailer wall bonds, wind turbine nacelle covers, railway interior panels, and composite structural reinforcements where weld-free assembly is required.
In cemented arthroplasty, the mixing of MMA liquid with PMMA-based powder is controlled by ISO 5833:2002 limits on maximum setting temperature, setting time, and compressive strength. The liquid component typically contains methyl methacrylate monomer at 85–90 wt%, N,N-dimethyl-p-toluidine accelerator at 0.5–1.5 wt%, and hydroquinone inhibitor at 20–80 ppm; the powder component contains PMMA or methyl methacrylate-styrene copolymer at 84–89 wt%, barium sulfate radiopacifier at 10 wt%, and benzoyl peroxide initiator at 0.5–1.5 wt%. The mixing ratio on the surgical line is 40 g powder to 20 mL liquid, combined in a vacuum cement mixer under -70 kPa to minimise porosity. Dough time is 1–2 min at 22 °C, working time is 3–6 min, and the cement is delivered into the femoral canal or tibial plateau through a cement gun before the polymerising mass reaches the high-viscosity plug stage. Temperature evolution is monitored because the polymerisation exotherm can exceed 90 °C, the ceiling specified in ISO 5833:2002; thick cement mantles and prewarmed components reduce working time and increase local exotherm risk. The finished interface is additionally tested according to ASTM F451-16 for acrylic bone cement, with minimum compressive strength specified at 70 MPa and bending modulus at 1,800 MPa. Terminal finished product types are cemented femoral stems, cemented tibial trays, acetabular cup fixation layers, vertebral augmentation cements, and cranioplasty templates where the balance between monomer volatility, setting time, and mechanical strength determines the acceptable implantation envelope.
| Standard parameter | Test reference | Limit in production-control records |
|---|---|---|
| Maximum polymerisation temperature | ISO 5833:2002 | ≤90 °C |
| Setting time | ISO 5833:2002 | 6.5–15 min |
| Compressive strength | ISO 5833:2002 | ≥70 MPa |
| Bending modulus | ASTM F451-16 | ≥1,800 MPa |
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Methyl methacrylate, CH2=C(CH3)COOCH3, is a clear mobile methacrylate ester with a molar mass of 100.12 g/mol, density 0.944 g/cm³ at 20 °C, viscosity 0.6 mPa·s at 20 °C, vapour pressure 3.9 kPa at 20 °C, normal boiling point 100.3 °C, closed-cup flash point 10 °C, autoignition temperature 421 °C, and explosion limits 2.1–12.5 vol % in air. Commercial bulk monomer is supplied as a chemical intermediate with ester content ≥ 99.5%, inhibited with monomethyl ether hydroquinone at 10–25 ppm; low-water and optical grades are produced for sheet casting and moulding applications where haze, water haze, and light transmittance are controlled. Methyl methacrylate is the principal raw material for poly(methyl methacrylate), acrylic copolymers, impact modifiers, dental resins, and reactive acrylic adhesives. Its flammability characteristics place storage and transfer operations under vapour-control and area-classification requirements.
Two commercial product forms dominate: inhibited bulk monomer for large-volume polymer production and formulated MMA-containing mixtures for specific engineering applications. The inhibited monomer is not a finished article; it is a reactive intermediate whose suitability depends on residual water, acid, inhibitor content, and colour. In acrylic sheet manufacturing, methyl methacrylate is polymerized in bulk cells or continuous casting lines. In waterborne coatings, it is introduced as a comonomer during emulsion polymerization. In PVC modification, it is incorporated during suspension polymerization of acrylic processing aids. These uses share the same monomer backbone but differ in required purity, inhibitor tolerance, and oxygen control.
The performance difference originates in side-chain length. Poly(methyl methacrylate) exhibits a glass transition temperature of 105 °C by differential scanning calorimetry under ISO 11357-2, while poly(butyl methacrylate) has a glass transition near 20 °C. The methyl ester group creates a denser chain conformation with higher tensile modulus and lower water absorption than the n-butyl ester, but it also raises the minimum film-forming temperature of aqueous dispersions measured under ISO 2115. A latex copolymer containing 40 wt% methyl methacrylate and 60 wt% n-butyl acrylate typically displays a glass transition near 5–10 °C according to the Fox relationship, although sequence distribution and conversion can shift the measured value. Reactivity also differs: methyl methacrylate has lower chain-transfer activity than butyl methacrylate because the n-butyl group provides additional abstractable hydrogen sites, leading to branching and molecular weight distribution shifts in high-conversion bulk polymerizations. In exterior coatings, acrylic binders are tested for chalking and film integrity under ASTM G154 and ASTM D4214; MMA-rich compositions are selected where higher hardness and UV resistance are required, whereas butyl methacrylate-rich compositions are selected for flexibility and low-temperature impact resistance.
| Property | Methyl methacrylate | n-Butyl methacrylate | Styrene |
|---|---|---|---|
| Molar mass | 100.12 g/mol | 142.20 g/mol | 104.15 g/mol |
| Normal boiling point | 100.3 °C | 160–163 °C | 145 °C |
| Density at 20 °C | 0.944 g/cm³ | 0.894 g/cm³ | 0.906 g/cm³ |
| Refractive index at 20 °C | 1.4140 | 1.4240 | 1.5460 |
| Homopolymer glass transition | 105 °C | 20 °C | 100 °C |
Bulk monomer is kept below 30 °C because inhibition depends on both MEHQ and dissolved oxygen. MEHQ in its quinone form traps propagating radicals, but oxygen must be present to regenerate the quinone; inert blanketing with nitrogen and no controlled oxygen addition can deactivate the inhibitor and permit slow radical accumulation. Storage tanks should be constructed from stainless steel or aluminium, with low-iron alloys preferred to avoid iron-catalysed peroxide decomposition. Copper and its alloys are incompatible because copper salts accelerate inhibitor consumption and produce coloured contaminants. Light exposure promotes peroxide formation, so outdoor tanks require light-excluding insulation or opaque coatings. At 45 °C, thermal initiation becomes measurable, and at 60–70 °C uninhibited monomer can enter a self-accelerating polymerization. The heat of polymerization is approximately 57.5 kJ/mol; in a closed vessel this exotherm can produce a rapid pressure rise if the relief system is not sized for a runaway polymerization rather than for fire exposure alone. Emergency relief design therefore uses adiabatic calorimetry data from accelerating rate calorimetry or vent sizing package testing, not simple vapour-pressure calculations. The practical storage boundary is narrow: with inhibitor at the lower specification limit of 10 ppm, a prolonged temperature excursion above 35 °C can consume the inhibitor inventory within weeks.
In continuous bulk polymerization for cast acrylic sheet, methyl methacrylate is mixed with 0.02–0.10 wt% of a free-radical initiator, usually azobisisobutyronitrile or lauroyl peroxide. The initiator selection is tied to half-life: azobisisobutyronitrile shows a 10-hour half-life near 64 °C in toluene, while lauroyl peroxide shows a 10-hour half-life near 62 °C. Cells are formed by two glass sheets separated by a flexible gasket and placed in a water bath programmed from 45–55 °C to 110–120 °C. During the gel effect, the centreline temperature can exceed the bath set point by more than 30 °C in sections thicker than 25 mm, producing optical haze and nonuniform shrinkage. Residual monomer after post-cure is reduced below 0.5 wt% to meet mechanical and sensory requirements. Extruded PMMA is produced from polymer rather than liquid monomer; twin-screw extruders with length-to-diameter ratios of 32:1 to 40:1 operate at melt temperatures of 230–260 °C with vacuum devolatilisation at downstream ports to strip residual monomer and moisture. In waterborne coatings, methyl methacrylate is copolymerized with n-butyl acrylate or 2-ethylhexyl acrylate at 30–45 wt% on total monomer; the resulting binder is evaluated under ASTM G154 for chalking resistance and ASTM D4585 for condensation resistance. In PVC processing, MMA-based acrylic processing aids are added at 1–5 phr to improve fusion, metal release, and melt strength during twin-screw extrusion.
Optical casting applies stricter limits than general-purpose bulk polymer. Methacrylic acid above 0.005 wt% can shift the polymerization sequence and increase water sensitivity; water above 0.05 wt% can hydrolyse monomer and initiator residues, releasing CO₂ and forming bubbles above 100 °C. Non-volatile oligomers and cross-linking impurities scatter light and reduce transmittance. For a 3 mm cast PMMA plaque, total luminous transmittance is measured under ISO 13468-1, and haze is measured under ISO 14782; optical grades typically require transmittance above 92% at 550 nm and haze below 0.5%. The gel-effect exotherm must be controlled within ±3 °C during the onset of autoacceleration to avoid visible density striations. Optical feedstock therefore includes additional incoming lot tests for particle count after 0.45 µm filtration, peroxide value, and UV absorption at 330 nm, even when ester content meets the bulk specification. These additional limits are not necessary for pigmented or filled PMMA, but the same impurities can cause defects in clear lenses, instrument covers, and light guides.
Commercial bulk methyl methacrylate is sold against a limited number of consensus parameters. The following values represent widely used tank-car and isotank specifications; individual supplier certificates should be consulted for lot-specific data.
| Parameter | Typical specification | Test method |
|---|---|---|
| Ester content | ≥ 99.5% | Gas chromatography, area normalisation |
| Water content | ≤ 0.05 wt% | ASTM E203 Karl Fischer titration |
| Acidity as methacrylic acid | ≤ 0.005 wt% | ASTM D1613 |
| Colour, Pt-Co | ≤ 10 APHA | ASTM D1209 |
| MEHQ inhibitor | 10–25 ppm | ASTM D3125 |
| Distillation range | 99.0–101.0 °C | ASTM D1078 |
| Density at 20 °C | 0.942–0.946 g/cm³ | ASTM D4052 |
Molecular weight control in bulk polymerization is achieved with chain transfer agents or with temperature selection; the choice depends on the desired melt flow rate. Melt mass-flow rate is determined under ISO 1133-1:2022 at 230 °C with 3.8 kg. Injection-moulding grades typically require melt mass-flow rates of 10–25 g/10 min, while extrusion grades are lower, near 1–4 g/10 min. Residual monomer levels above 0.5 wt% depress the onset of thermal degradation during melt processing and increase plate-out on mould surfaces. This trade-off between molecular weight and residual monomer is a central control parameter in continuous bulk processes.
Polymerized methyl methacrylate used in food-contact articles is addressed in the United States under FDA 21 CFR 177.1010 for semi-rigid and rigid acrylic plastics. In the European Union, PMMA food-contact articles are evaluated under Commission Regulation (EU) No 10/2011, with overall migration testing and specific migration controls for unconverted methyl methacrylate. Occupational exposure to the monomer is controlled under OSHA 29 CFR 1910.1000 Table Z-1, with an 8-hour time-weighted average permissible exposure limit of 100 ppm (410 mg/m³); the current ACGIH threshold limit value is 50 ppm with skin notation. The monomer is flammable and reactive; unvented containers, spill containment, and static discharge controls are part of transfer operations. Incompatible materials include amine-based additives, strong bases, and copper compounds, which either deplete inhibitor or accelerate radical generation.
Although both monomers produce high-glass-transition homopolymers, their behaviour in aqueous emulsion polymerization is not equivalent. Methyl methacrylate has higher water solubility than styrene, increasing radical exit from particles and altering nucleation kinetics; this property also influences residual monomer stripping. Styrene contributes lower water absorption and higher refractive index, while methyl methacrylate contributes better resistance to photoyellowing when evaluated under ASTM G154 colour retention protocols. In masonry coatings, terpolymers containing methyl methacrylate, n-butyl acrylate, and styrene are formulated at 25–35 wt% MMA to achieve adhesion, hardness, and weather resistance; dirt pickup is evaluated under ASTM D3719. Reactor fouling is more common with MMA-rich recipes because the monomer is less water-soluble than lower acrylate monomers and can form polymer deposits on baffles and thermowells if pre-emulsion feed interruption occurs. Residual monomer stripping under vacuum at 80–85 °C reduces free monomer levels in the final latex.
