80-62-6 Usage
Uses
Used in Plastics and Resins Industry:
Methyl methacrylate is used as a principal component in the production of cast acrylic sheet, acrylic emulsions, and molding and extrusion resins. It is also utilized in the manufacture of methacrylate resins and plastics, where it undergoes transesterification into higher methacrylates such as n-butyl methacrylate or 2-ethylhexyl methacrylate.
Used in Coating and Adhesive Industry:
Methyl methacrylate polymers and copolymers are used in waterborne, solvent, and undissolved surface coatings, adhesives, sealants, leather and paper coatings, inks, and floor polishes.
Used in Textile and Dental Industry:
Methyl methacrylate is employed in textile finishes and dental prostheses, as well as in the production of surgical bone cements and leaded acrylic radiation shields.
Used in Medical and Orthopedic Industry:
Methyl methacrylate serves as a cement in total hip and knee replacements, acting as a grout to fix bone inserts and reduce post-operative pain. It has a typical lifespan of 20 years before revision surgery is needed.
Used in Automotive and Electronics Industry:
Granules of methyl methacrylate are used in injection and extrusion blow molding for their outstanding optical clarity, weathering, and scratch resistance in applications such as lighting, office equipment, electronics, building and construction, contemporary design, cars, transportation, health and safety, and household appliances.
Used in Chemical Production:
Methyl methacrylate is used as a starting material to manufacture other esters of methacrylic acid and serves as an impact modifier for clear rigid polyvinyl chloride.
Used in Orthopedic Surgery:
Methyl methacrylate is utilized in acrylic bone cements for orthopedic surgery and in fracture repair in small exotic animal species using internal fixation.
Used in Various Applications:
Methyl methacrylate is also used in the production of acrylic polymers, polymethylmethacrylate and copolymers for acrylic surface coatings, emulsion polymers, modification of unsaturated polyester resins, higher methacrylate, acrylic fibers, acrylic film, inks, radiation-polymerized impregnants for wood, solvent-based adhesives and binders, medicinal spray adhesives, nonirritant bandage solvents, dental technology as ceramic filler or cement, coating of corneal contact lenses, intraocular lenses, artificial nails, and hearing aids, and in the impregnation of concrete.
Production Methods
Methyl methacrylate (MMA) is the most important ester of methacrylic acid. It can be homo- and copolymerised to produce acrylic resins with good strength, transparency and with excellent weather resistance. The first commercial process for making MMA (1930's), the acetone cyanohydrin route, remains the predominant process in use today. In the acetone cyanohydrin route, acetone cyanohydrin reacts with sulfuric acid at low temperature to produce the sulfuric monoester of 2-hydroxy-2-methyl-propionamide, which forms methacrylamide sulphate after exposure to higher temperatures (100° - 140°C). The liquid phase is maintained by using an excess of 0.2 - 0.7 moles of 100% sulfuric acid. The first step of the reaction is strongly exothermic while the rearrangement of the sulfuric ester is endothermic.
During the synthesis of methacrylamide, a portion of the acetone cyanohydrin decomposes to carbon monoxide during the first part of the reaction. Additionally other by-products are formed and react due to the strength of the acid and high temperature in the second step. About 92 - 94% of the acetone cyanohydrin is converted to useful products and 6 - 8% is consumed in the formation of organic by-products (acetone, acetone sulphonates, olygomers, polymers, others). Methacrylamide sulphate is esterified with a mixture of water and methanol to form MMA and an aqueous solution of ammonium hydrogensulphate, sulfuric acid and the organic by-products. The ammonium hydrogensulphate is an unavoidable by-product of the reaction.
Production Methods
The compound is manufactured by several methods, the principal one being the acetone cyanohydrin (ACH) route, using acetone and hydrogen cyanide as raw materials. The intermediate cyanohydrin is converted with sulfuric acid to a sulfate ester of the methacrylamide, methanolysis of which gives ammonium bisulfate and MMA. Although widely used, the ACH route coproduces substantial amounts of ammonium sulfate. Some producers start with an isobutylene or, equivalently, tert-butanol, which is sequentially oxidized first to methacrolein and then to methacrylic acid, which is then esterified with methanol. Propene can be carbonylated in the presence of acids to iso butyric acid, which undergoes subsequent dehydrogenation . The combined technologies afford more than 3 billion kilograms per year. MMA can also be prepared from methyl propionate and formaldehyde.
Preparation
Prepared by the esterification of methacrylamide sulfate with methanol.
Synthesis Reference(s)
Journal of the American Chemical Society, 70, p. 1153, 1948 DOI: 10.1021/ja01183a082The Journal of Organic Chemistry, 33, p. 2525, 1968 DOI: 10.1021/jo01270a082
Reactivity Profile
Methyl methacrylate, may polymerize if contaminated or subjected to heat. If polymerization takes place in a container, the container is subject to violent rupture. Oxidizes readily in air to form unstable peroxides that may explode spontaneously [Bretherick 1979. p.151-154, 164]. Peroxides may also initiate exothermic polymierization of the bulk material [Bretherick 1979. p. 160]. Benzoyl peroxide was weighed into a beaker that had previously been rinsed with methyl methacrylate. The peroxide catalyzed polymerization of the methyl methacrylate and the build-up of heat ignited the remaining peroxide [MCA Case History 996. 1964].
Hazard
Flammable, dangerous fire risk, explosivelimits in air 2.1–12.5%. Eye and upper respiratorytract irritant, body weight effects, and pulmonaryedema. Questionable carcinogen.
Health Hazard
Methyl methacrylate may cause slight eye irritation or moderate skin irritation. It is considered a skin sensitizer; allergic reactions may result from contact. Inhalation of vapor or mist can cause irritation of the nose, throat, and lungs and can be fatal in high concentrations. Prolonged or repeated overexposure has been reported to affect the kidneys, liver, gastrointestinal tract, nervous system and lung.
Methyl methacrylate is moderately toxic to aquatic organisms on an acute basis. The bioconcentration potential (tendency to accumulate in the food chain) is low. If released to surface water, methyl methacrylate will readily biodegrade. A portion may evaporate to the air. It will not persist in the environment.
Irritation of eyes, nose, and throat. Nausea and vomiting. Liquid may cause skin irritation.
Fire Hazard
Behavior in Fire: Vapor is heavier than air and may travel a considerable distance to a source of ignition and flash back. Containers may explode in fire or when heated because of polymerization.
Flammability and Explosibility
Flammable
Safety Profile
Moderately toxic by
inhalation and intraperitoneal routes. Mildly
toxic by ingestion. Human systemic effects
by inhalation: sleep effects, excitement,
anorexia, and blood pressure decrease.
Experimental teratogenic and reproductive
effects. Mutation data reported. A skin and
eye irritant. Questionable carcinogen with
experimental tumorigenic data. A common
air contaminant.
A very dangerous fire hazard when
exposed to heat or flame; can react with
oxidizing materials. Explosive in the form of
vapor when exposed to heat or flame. The
monomer may undergo spontaneous,
explosive polymerization. Reacts in air to
form a heat-sensitive explosive product
(explodes on evaporation at 6OOC). May
ignite on contact with benzoyl peroxide.
Potentially violent reaction with the
polymerization initiators azoisobutyronitrile,
dibenzoyl peroxide, di-tert-butyl peroxide,
propionaldehyde. To fight fire, use foam,
CO2, dry chemical. When heated to
decomposition it emits acrid smoke and
irritating fumes.
Potential Exposure
Virtually all of the methyl methacrylate monomer produced is used in the production of
polymers, such as surface coating resins; plastics (Plexiglas
and Lucite); ion exchange resins; and plastic dentures.
Carcinogenicity
In several lifetime animal studies,
there was no evidence that methyl methacrylate is
carcinogenic.
Environmental fate
Chemical/Physical. Polymerizes easily (Windholz et al., 1983). Methyl methacrylate undergoes
nucleophilic attack by OH ions in water (hydrolysis) resulting in the formation of methacrylic acid
and methanol (Kollig, 1993). Hydrolysis occurs at a rate of 171/M?h at 25 °C (Sharma and
Sharma, 1970). No measurable hydrolysis was observed at 85.0 °C (pH 7) and 25 °C (pH 7.07).
Hydrolysis half-lives of 9 and 134 min were observed at 66.0 °C (pH 9.86) and 25.0 °C (pH 11.3),
respectively (Ellington et al., 1987).
storage
Methyl methacrylate is a reactive chemical that must be stored and handled with care. It is stable under recommended storage conditions. Heat can cause polymerization. Inhibitor is added to methyl methacrylate monomer to prevent polymerization. For the inhibitor to be effective, the oxygen concentration in the vapor space must be at least 5%. Store material in containers made of stainless steel, carbon steel, glass, or aluminum. Avoid contact with acids, bases, oxidizing agents, reducing agents, UV light (ultraviolet light, which is found in sunlight), free-radical initiators, and organic peroxides.
Shipping
UN1247 Methyl methacrylate monomer,
stabilized, Hazard Class: 3; Labels: 3-Flammable liquid.
Purification Methods
Wash the ester twice with aqueous 5% NaOH (to remove inhibitors such as hydroquinone) and twice with water. Dry it with CaCl2, Na2CO3, Na2SO4 or MgSO4, then with CaH2 under nitrogen under reduced pressure. The distillate is stored at low temperatures and redistilled before use. Prior to distilling, inhibitors such as hydroquinone (0,004%), .-naphthylamine (0.2%) or di--naphthol are sometimes added. Also purify it by boiling with aqueous H3PO4 solution and finally with saturated NaCl solution. It is dried for 24hours over anhydrous CaSO4, distilled at 0.1mm Hg at room temperature and stored at -30o [Albeck et al. J Chem Soc, Faraday Trans 1 1 1488 1978]. [Beilstein 2 II 398, 2 III 1279, 2 IV 1519.]
Toxicity evaluation
The mitochondria are regarded as the main intracellular
target of MMA. If isolated rat liver mitochondria are incubated
with MMA, oxygen consumption increases. This is
the result of an uncoupling of the mitochondrial respiratory
chain, as seen from the expected influence on state 4
and state 3 respiration. State 4 respiration is stimulated. As
has been reported for organic solvents, MMA attacks
complex I of the respiratory chain close to the rotenonebinding
site. This means that substrates which are oxidized
in conjunction with nicotinamide adenine dinucleotide
inhibit the flow of electrons and thus also ATP synthesis.
Unlike classical uncouplers, MMA stimulates the Mg2+-
dependent ATPase bound to the inner mitochondrial membrane.
Structural changes in the inner membrane, as found
with nonionic detergents, were observed by electron micro
scopy. The release of enzymes indicates disintegration of
the membrane.
Incompatibilities
Vapor may form explosive mixture
with air. Reacts in air to form a heat-sensitive explosive
product @ 60C. Incompatible with nitrates, oxidizers,
peroxides, strong acids; strong alkalis; oxidizers,
reducing agents; amines, moisture. Contact with benzoyl
peroxide may cause ignition, fire and explosion. May
polymerize if subjected to heat, polymerization catalysts
e. g., azoisobutyronitrile, dibenzoyl peroxide; di-tert-butyl
peroxide, propionaldehyde); strong oxidizers; or ultraviolet light. May contain an inhibitor, such as hydroquinone.
Waste Disposal
Consult with environmental
regulatory agencies for guidance on acceptable disposal
practices. Generators of waste containing this contaminant
(≥100 kg/mo) must conform to EPA regulations governing
storage, transportation, treatment, and waste disposal.
Incineration may be allowed.
Check Digit Verification of cas no
The CAS Registry Mumber 80-62-6 includes 5 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 2 digits, 8 and 0 respectively; the second part has 2 digits, 6 and 2 respectively.
Calculate Digit Verification of CAS Registry Number 80-62:
(4*8)+(3*0)+(2*6)+(1*2)=46
46 % 10 = 6
So 80-62-6 is a valid CAS Registry Number.
InChI:InChI=1/C5H8O2/c1-4(2)5(6)7-3/h1H2,2-3H3
80-62-6Relevant articles and documents
Multicatalytic Transformation of (Meth)acrylic Acids: a One-Pot Approach to Biobased Poly(meth)acrylates
Fouilloux, Hugo,Placet, Vincent,Qiang, Wei,Robert, Carine,Thomas, Christophe M.
supporting information, p. 19374 - 19382 (2021/07/21)
Shifting from petrochemical feedstocks to renewable resources can address some of the environmental issues associated with petrochemical extraction and make plastics production sustainable. Therefore, there is a growing interest in selective methods for transforming abundant renewable feedstocks into monomers suitable for polymer production. Reported herein are one-pot catalytic systems, that are active, productive, and selective under mild conditions for the synthesis of copolymers from renewable materials. Each system allows for anhydride formation, alcohol acylation and/or acid esterification, as well as polymerization of the formed (meth)acrylates, providing direct access to a new library of unique poly(meth)acrylates.
The effect of viscosity on the coupling and hydrogen-abstraction reaction between transient and persistent radicals
Li, Xiaopei,Kato, Tatsuhisa,Nakamura, Yasuyuki,Yamago, Shigeru
, p. 966 - 972 (2021/04/29)
The effect of viscosity on the radical termination reaction between a transient radical and a persistent radical undergoing a coupling reaction (Coup) or hydrogen abstraction (Abst) was examined. In a non-viscous solvent, such as benzene (bulk viscosity bulk 99% Coup/Abst selectivity, but Coup/Abst decreased as the viscosity increased (89/11 in PEG400 at 25 °C [bulk = 84 mPa s]). While bulk viscosity is a good parameter to predict the Coup/Abst selectivity in each solvent, microviscosity is the more general parameter. Poly(methyl methacrylate) (PMMA)-end radicals had a more significant viscosity effect than polystyrene (PSt)-end radicals, and the Coup/Abst ratio of the former dropped to 50/50 in highly viscous media (bulk = 3980 mPa s), while the latter maintained high Coup/ Abst selectivity (84/16). These results, together with the low thermal stability of dormant PMMA-TEMPO species compared with that of PSt-TEMPO species, are attributed to the limitation of the nitroxide-mediated radical polymerization of MMA. While both organotellurium and bromine compounds were used as precursors of radicals, the former was superior to the latter for the clean generation of radical species.
A CATALYST AND A PROCESS FOR THE PRODUCTION OF ETHYLENICALLY UNSATURATED CARBOXYLIC ACIDS OR ESTERS
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Page/Page column 40, (2021/02/05)
The invention discloses a catalyst comprising a silica support, a modifier metal and a catalytic alkali metal. The silica support has a multimodal pore size distribution comprising a mesoporous pore size distribution having an average pore size in the range 2 to 50 nm and a pore volume of said mesopores of at least 0.1 cm3/g, and a macroporous pore size distribution having an average pore size of more than 50 nm and a pore volume of said macropores of at least 0.1 cm3/g. The level of catalytic alkali metal on the silica support is at least 2 mol%. The modifier metal is selected from Mg, B, Al, Ti, Zr and Hf. The invention also discloses a method of producing the catalyst, a method of producing an ethylenically unsaturated carboxylic acid or ester in the presence of the catalyst, and a process for preparing an ethylenically unsaturated acid or ester in the presence of the catalyst.
Gold-based catalyst for oxidative esterification of aldehydes to carboxylic acid esters
-
Page/Page column 15, (2021/02/03)
The present invention relates to novel catalysts for oxidative esterification, by means of which, for example, (meth)acrolein can be converted to methyl (meth)acrylate. The catalysts of the invention are especially notable for high mechanical and chemical stability even over very long periods. This especially relates to an improvement in the catalyst service life, activity and selectivity over prior art catalysts which lose activity and/or selectivity relatively quickly in continuous operation in media having even a small water content.
The effect of the bimetallic Pd-Pb structures on direct oxidative esterification of methacrolein with methanol
Diao, Yanyan,Qi, Miao,Song, Yuting,Wang, Ling,Wu, Xiangying
, (2021/06/28)
Supported palladium and palladium alloy were proved to be active catalysts for the oxidative esterification reaction of methacrolein with methonal to methyl methacrylate. Here we synthesized two types of structurally supported palladium alloy catalysts with ordered or disordered Pd3Pb intermetallic crystals by impregnation-reduction method as well as high temperature heat treatment. Importantly, the catalyst with disordered Pd3Pb crystals had 89% conversion for methylacrolein and 79% selectivity for methyl methacrylate, showing obvious higher activity than the catalyst with ordered Pd3Pb crystals. The morphology, metal arrangement and electron effect of the catalyst were analyzed by XRD, TEM and XPS. It was confirmed that more active sites and strong electron transfer between metals were the reasons for the excellent performance of the disordered catalyst. This study provides theoretical guidance for the further study of Pd-based catalysts for the oxidative esterification of methacrolein to methyl methacrylate.
Esterification or Thioesterification of Carboxylic Acids with Alcohols or Thiols Using Amphipathic Monolith-SO3H Resin
Ichihara, Shuta,Ishida, Moeka,Ito, Ryo,Kato, Ayumu,Monguchi, Yasunari,Nakamura, Shinji,Park, Kwihwan,Sajiki, Hironao,Takada, Hitoshi,Wakayama, Fumika,Yamada, Tsuyoshi,Yamada, Yutaro
, p. 2702 - 2710 (2022/01/19)
We have developed a method for the esterification of carboxylic acids with alcohols using amphipathic, monolithic-resin bearing sulfonic acid moieties as cation exchange functions (monolith-SO3H). Monolith-SO3H efficiently catalyzed the esterification of aromatic and aliphatic carboxylic acids with various primary and secondary alcohols (1.55.0 equiv) in toluene at 6080 °C without the need to remove water generated during the reaction. The amphipathic property of monolith-SO3H facilitates dehydration due to its capacity for water absorption. This reaction was also applicable to thioesterification, wherein the corresponding thioesters were obtained in excellent yield using only 2.0 equiv of thiol in toluene, although heating at 120 °C was required. Moreover, monolith-SO3H was separable from the reaction mixtures by simple filtration and reused for at least five runs without decreasing the catalytic activity.
A PROCESS FOR THE PRODUCTION OF A CATALYST, A CATALYST THEREFROM AND A PROCESS FOR PRODUCTION OF ETHYLENICALLY UNSATURATED CARBOXYLIC ACIDS OR ESTERS
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Page/Page column 31-32, (2020/09/30)
The present invention relates to a process for producing a catalyst. The process comprises the steps of: a) providing an uncalcined metal modified porous silica support wherein the modifier metal is selected from one or more of boron, magnesium, aluminium, zirconium, hafnium and titanium, wherein the modifier metal is present in mono- or dinuclear modifier metal moieties; b) optionally removing any solvent or liquid carrier from the modified silica support; c) optionally drying the modified silica support; d) treating the uncalcined metal modified silica support with a catalytic metal to effect adsorption of the catalytic metal onto the metal modified silica support; and e) calcining the impregnated silica support of step d). The invention extends to an uncalcined catalyst intermediate and a method of producing a catalyst by providing a porous silica support having isolated silanol groups.
HETEROGENEOUS CATALYST
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Page/Page column 5-7, (2020/01/24)
A heterogeneous catalyst comprising a support and gold, wherein: (i) said support comprises alumina, (ii) said catalyst comprises from 0.1 to 5 wt% of gold, (iii) at least 90 wt% of the gold is in the outer 60% of catalyst volume, and (iv) particles of the catalyst have an average diameter from 200 microns to 30 mm; wherein weight percentages are based on weight of the catalyst. The catalyst of this invention is used in a process for producing methyl methacrylate (MMA) which comprises treating methacrolein with methanol in an oxidative esterification reactor.
Method for carrying out a heterogeneously catalysed reaction
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Page/Page column 8-10, (2020/04/09)
A process for performing a heterogeneously catalysed reaction in a three-phase reactor, where there is at least one liquid phase, at least one gaseous phase and at least one solid phase in the reactor and the reactor has at least two zones, with the reaction mixture being conveyed downward in zone 1, the reaction mixture being conveyed upward in zone 2, zones 1 and 2 being separated from one another by a dividing wall, and in that the ratio between the average catalyst concentrations in zone 2 and in zone 1 is greater than 2.
Second-Generation meta-Phenolsulfonic Acid-Formaldehyde Resin as a Catalyst for Continuous-Flow Esterification
Hu, Hao,Ota, Hajime,Baek, Heeyoel,Shinohara, Kenta,Mase, Toshiaki,Uozumi, Yasuhiro,Yamada, Yoichi M. A.
supporting information, p. 160 - 163 (2020/01/02)
A second-generation m-phenolsulfonic acid-formaldehyde resin (PAFR II) catalyst was prepared by condensation polymerization of sodium m-phenolsulfonate and paraformaldehyde in an aqueous H2SO4 solution. This reusable, robust acid resin catalyst was improved in both catalytic activity and stability, maintaining the characteristics of the previous generation catalyst (p-phenolsulfonic acid-formaldehyde resin). PAFR II was applied in the batchwise and continuous-flow direct esterification without water removal and provided higher product yields in continuous-flow esterification than any other commercial ion-exchanged acid catalyst tested.
