Chemistry:Methyl methacrylate

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Short description: Organic monomer
Not to be confused with methyl acrylate.
Methyl methacrylate
Methyl methacrylate
Names
Preferred IUPAC name
Methyl 2-methylprop-2-enoate
Other names
Methyl 2-methylpropenoate
methyl methacrylate
MMA
2-(methoxycarbonyl)-1-propene
Identifiers
3D model (JSmol)
605459
ChEBI
ChEMBL
ChemSpider
EC Number
  • 201-297-1
2691
KEGG
RTECS number
  • OZ5075000
UNII
UN number 1247
Properties
C5H8O2
Molar mass 100.117 g·mol−1
Appearance Colorless liquid
Odor acrid, fruity[1]
Density 0.94 g/cm3
Melting point −48 °C (−54 °F; 225 K)
Boiling point 101 °C (214 °F; 374 K)
1.5 g/100 ml
log P 1.35 [2]
Vapor pressure 29 mmHg (20 °C)[1]
−57.3·10−6 cm3/mol
Viscosity 0.6 cP at 20 °C
Structure
1.6–1.97 D
Hazards
Main hazards Flammable
GHS pictograms GHS02: FlammableGHS07: Harmful
GHS Signal word Danger
H225, H315, H317, H335
P210, P233, P240, P241, P242, P243, P261, P264, P271, P272, P280, P302+352, P303+361+353, P304+340, P312, P321, P332+313, P333+313, P362, P363, P370+378, P403+233, P403+235, P405, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondFlammability code 3: Liquids and solids that can be ignited under almost all ambient temperature conditions. Flash point between 23 and 38 °C (73 and 100 °F). E.g. gasolineHealth code 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformReactivity (yellow): no hazard codeSpecial hazards (white): no code
3
2
Flash point 2 °C (36 °F; 275 K)
435 °C (815 °F; 708 K)
Explosive limits 1.7%-8.2%[1]
Lethal dose or concentration (LD, LC):
8420-10000 mg/kg (rat, oral)
5000-7500 mg/kg (rabbit, dermal)
18750 ppm (rat, 4 hr)
4447 ppm (mouse, 2 hr)
3750 ppm (rat)
4808 ppm (mammal)[3]
4400 ppm (rat, 8 hr)
4400 ppm (rabbit, 8 hr)
4207 ppm (rabbit, 4.5 hr)
4567 ppm (guinea pig, 5 hr)[3]
NIOSH (US health exposure limits):
PEL (Permissible)
 TWA 100 ppm (410 mg/m3)[1]
REL (Recommended)
 TWA 100 ppm (410 mg/m3)[1]
IDLH (Immediate danger)
 1000 ppm[1]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references
Tracking categories (test):

Methyl methacrylate (MMA) is an organic compound with the formula CH
2=C(CH
3)COOCH
3. This colorless liquid, the methyl ester of methacrylic acid (MAA), is a monomer produced on a large scale for the production of poly(methyl methacrylate) (PMMA).[4]

History

MMA was discovered by Bernhard Tollens and his student W. A. Caspary in 1873,[5] who noticed and described its tendency to change into a clear, hard, transparent substance especially in sunlight.[6] Studies on acrylic esters slowly developed until the Staudinger's theory of macromolecules and his research into the nature of polyacrylates allowed control over polymerization. Company Rohm and Haas founded by German chemist Otto Röhm, who investigated the topic for three decades, was finally able to start its industrial production in 1931.[7]

Production and properties

Given the scale of production, many methods have been developed starting from diverse two- to four-carbon precursors.[8] Two principal routes appear to be commonly practiced.

Cyanohydrin route

The principal route begins with the condensation of acetone and hydrogen cyanide:[4]

(CH
3)
2CO + HCN → (CH
3)
2C(OH)CN

Sulfuric acid then hydrolyzes acetone cyanohydrin (ACH) to a sulfate ester-adduct, which is cracked to the ester:

(CH
3)
2C(OH)CN + 2H
2SO
4 → ((CH
3)
2C(OSO
3H)C(O)NH
2·H
2SO
4 → (CH
3)
2C(OSO
3H)C(O)NH
2 + H
2SO
4

Methanolysis gives ammonium bisulfate and MMA:

(CH
3)
2C(OSO
3H)C(O)NH
2 + CH
3OH → CH
2=C(CH
3)C(O)OCH
3 + NH
4HSO
4

Laboratory scale procedures are available for some of these steps.[9]

This technology affords more than 3 billion kilograms per year, and the economics have been optimized.[10][11] Nevertheless, the ACH route coproduces substantial amounts of ammonium sulfate: roughly 1.1 kg/(kg MMA). The ammonium sulfate can be converted to diammonium sulfate, which is a common fertilizer. Also it can be combusted to give sulfuric acid.

Methyl propionate routes

The first stage involves carboalkoxylation of ethylene to produce methyl propionate (MeP):[12]

C
2H
4 + CO + CH
3OH → CH
3CH
2CO
2CH
3

The MeP synthesis is conducted in a continuous-stirred tank reactor at moderate temperature and pressure using proprietary agitation and gas-liquid mixing arrangement.

In a second set of reactions, MeP is condensed with formaldehyde in a single heterogeneous reaction step to form MMA:[13]

CH
3CH
2CO
2CH
3 + CH
2O → CH
3(CH
2)CCO
2CH
3 + H
2O

The reaction of MeP and formaldehyde takes place over a fixed bed of catalyst. This catalyst, caesium oxide on silica, achieves good selectivity to MMA from MeP. The formation of a small amount of heavy, relatively involatile compounds poisons the catalyst. The coke is easily removed and catalyst activity and selectivity restored by controlled, in-situ regeneration. The reactor product stream is separated in a primary distillation so that a crude MMA product stream, free from water, MeP and formaldehyde, is produced. Unreacted MeP and water are recycled via the formaldehyde dehydration process. MMA (>99.9%) is purified by vacuum distillations. The separated streams are returned to the process; there being only a small heavy ester purge stream, which is disposed of in a thermal oxidizer with heat recovered for use in the process.

In 2008, Lucite International commissioned an Alpha MMA plant on Jurong Island in Singapore. This process plant was cheaper to build and run than conventional systems, produces virtually no waste and the feedstocks can even be made from biomass.

Other routes to MMA

Via propionaldehyde

Ethylene is first hydroformylated to give propanal, which is then condensed with formaldehyde to produce methacrolein, The condensation is catalyzed by a secondary amine. Air oxidation of methacrolein to methacrylic acid completes the synthesis of the acid:[10]

CH
3CH
2CHO + HCHO → CH
2=C(CH
3)CHO + H
2O
CH
2=C(CH
3)CHO + ½ O
2 → CH
2=C(CH
3)CO
2H

From isobutyric acid

As developed by Atochem and Röhm, isobutyric acid is produced by hydrocarboxylation of propene, using HF as a catalyst:

CH
2=CHCH
3 + CO + H
2O → (CH
3)
2CHCO
2H

Oxidative dehydrogenation of the isobutyric acid yields methacrylic acid. Metal oxides catalyse this process:[10]

(CH
3)
2CHCO
2H + O → CH
2=C(CH
3)CO
2H + H
2O

Methyl acetylene (propyne) process

Using Reppe chemistry, methyl acetylene is converted to MMA. As developed by Shell, this process produces MMA in one step reaction with 99% yield with a catalyst derived from palladium acetate, phosphine ligands, and Bronsted acids as catalyst:[10]

CH≡CCH
3 + CO + CH
3OH → CH
2=C(CH
3)CO
2CH
3

Isobutylene routes

The reactions by the direct oxidation method consist of two-step oxidation of isobutylene or TBA with air to produce methacrylic acid and esterification by methanol to produce MMA.[10]

CH
2=C(CH
3)
2
or (CH
3)
3C–OH + O
2 → CH
2=C(CH
3)–CHO + H
2O
CH
2=C(CH
3)CHO + ½ O
2 → CH
2=C(CH
3)CO
2H
CH
2=C(CH
3)CO
2H + CH
3OH → CH
2=C(CH
3)CO
2CH
3 + H
2O

A process using isobutylene as a raw material has been commercialized by Escambia Co. Isobutylene is oxidized to provide α-hydroxy isobutyric acid. The conversion uses N
2O
4 and nitric acid at 5–10 °C in the liquid phase. After esterification and dehydration MMA is obtained. Challenges with this route, aside from yield, involve the handling of large amounts of nitric acid and NO
x. This method was discontinued in 1965 after an explosion at an operation plant.[10]

Methacrylonitrile (MAN) process

MAN can be produced by ammoxidation from isobutylene:

(CH
3)
2C=CH
2 + NH
3 + 3
/
2 O
2 → CH
2=C(CH
3)CN + 3 H
2O

This step is analogous to the industrial route to acrylonitrile, a related commodity chemical. MAN can be hydrated by sulfuric acid to methacrylamide:

CH
2=C(CH
3)CN + H
2SO
4 + H
2O → CH
2=C(CH
3)–CONH
2 · H
2SO
4
CH
2=C(CH
3)–CONH
2 · H
2SO
4 + CH
3OH → CH
2=C(CH
3)COOCH
3 + NH
4HSO
4

Mitsubishi Gas Chemicals proposed that MAN can be hydrated to methacrylamide without using sulfuric acid and is then esterified to obtain MMA by methylformate.[10]

CH
2=C(CH
3)CN + H
2O → CH
2=C(CH
3)–CONH
2
CH
2=C(CH
3)–CONH
2 + HCOOCH
3 → CH
2=C(CH
3)COOCH
3 + HCONH
2
HCONH
2 → NH
3 + CO

Esterification of methacrolein

Asahi Chemical developed a process based on direct oxidative esterification of methacrolein, which does not produce by-products such as ammonium bisulfate. The raw material is tert-butanol, as in the direct oxidation method. In the first step, methacrolein is produced in the same way as in the direct oxidation process by gas phase catalytic oxidation, is simultaneously oxidized and is esterified in liquid methanol to get MMA directly.[10]

CH
2=C(CH
3)–CHO + CH
3OH + ½ O
2 → CH
2=C(CH
3)–COOCH
3 + H
2O

Uses

The principal application, consuming approximately 75% of the MMA, is the manufacture of polymethyl methacrylate acrylic plastics (PMMA). Methyl methacrylate is also used for the production of the co-polymer methyl methacrylate-butadiene-styrene (MBS), used as a modifier for PVC. Another application is as cement used in total hip replacements as well as total knee replacements. Used as the "grout" by orthopedic surgeons to make the bone inserts fix into bone, it greatly reduces post-operative pain from the insertions but has a finite lifespan. Typically the lifespan of methylmethacrylate as bone cement is 20 years before revision surgery is required. Cemented implants are usually only done in elderly populations that require more immediate short term replacements. In younger populations, cementless implants are used because their lifespan is considerably longer.[14] Also used in fracture repair in small exotic animal species using internal fixation.

MMA is a raw material for the manufacture of other methacrylates. These derivatives include ethyl methacrylate (EMA), butyl methacrylate (BMA) and 2-ethyl hexyl methacrylate (2-EHMA). Methacrylic acid (MAA) is used as a chemical intermediate as well as in the manufacture of coating polymers, construction chemicals and textile applications.[15]

Wood can be impregnated with MMA and polymerized in situ to produce stabilized wood.

MMA is the raw material in many adhesives. They have advantages over other adhesives in that they show a good degree of surface tolerance, rapid drying and flexibility. [16]

Environmental issues and health hazards

In terms of the acute toxicity of methyl methacrylate, the LD50 is 7–10 g/kg (oral, rat). It is an irritant to the eyes and can cause redness and pain.[17][18] Irritation of the skin, eye, and nasal cavity has been observed in rodents and rabbits exposed to relatively high concentrations of methyl methacrylate. Methyl methacrylate is a mild skin irritant in humans and has the potential to induce skin sensitization in susceptible individuals.[19][20]

See also

References

  1. ↑ 1.0 1.1 1.2 1.3 1.4 1.5 NIOSH Pocket Guide to Chemical Hazards. "#0426". National Institute for Occupational Safety and Health (NIOSH). https://www.cdc.gov/niosh/npg/npgd0426.html. 
  2. ↑ "Methyl methacrylate". https://www.chemsrc.com/en/cas/80-62-6_32386.html. 
  3. ↑ 3.0 3.1 "Methyl methacrylate". Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH). https://www.cdc.gov/niosh/idlh/80626.html. 
  4. ↑ 4.0 4.1 Bauer, Jr., William (2002). "Ullmann's Encyclopedia of Industrial Chemistry". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a16_441. 
  5. ↑ Caspary, W.; Tollens, B. (January 1873). "Ueberführung der β-Bibrompropionsäure in Acrylsäure" (in en). Justus Liebigs Annalen der Chemie 167 (2): 240–257. doi:10.1002/jlac.18731670208. ISSN 0075-4617. https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/jlac.18731670208. 
  6. ↑ "New series: Acrylic patented 90 years ago" (in en). https://www.k-online.com/en/Media_News/News/April_2018_Acrylic_patented_90_years_ago_(Part_1)/New_series_Acrylic_patented_90_years_ago. 
  7. ↑ Neher, Harry T. (March 1936). "Acrylic Resins" (in en). Industrial & Engineering Chemistry 28 (3): 267–271. doi:10.1021/ie50315a002. ISSN 0019-7866. https://pubs.acs.org/doi/abs/10.1021/ie50315a002. 
  8. ↑ Darabi Mahboub, Mohammad Jaber; Dubois, Jean-Luc; Cavani, Fabrizio; Rostamizadeh, Mohammad; Patience, Gregory S. (2018). "Catalysis for the synthesis of methacrylic acid and methyl methacrylate". Chemical Society Reviews 47 (20): 7703–7738. doi:10.1039/C8CS00117K. PMID 30211916. 
  9. ↑ Wiley, Richard H.; Waddey, Walter E. (1949). "Methacrylamide". Organic Syntheses 29: 61. doi:10.15227/orgsyn.029.0061. 
  10. ↑ 10.0 10.1 10.2 10.3 10.4 10.5 10.6 10.7 Nagai, Koichi (2001). "New developments in the production of methyl methacrylate". Applied Catalysis A: General 221 (1–2): 367–377. doi:10.1016/S0926-860X(01)00810-9. Bibcode: 2001AppCA.221..367N. 
  11. ↑ "New Catalyst for Methyl Methacrylate Process :: News". 22 August 2012. http://www.chemistryviews.org/details/news/2502791/New_Catalyst_for_Methyl_Methacrylate_Process.html. 
  12. ↑ Scott D. Barnicki (2012). "Chapter 10. Synthetic Organic Chemicals". in James A. Kent. Handbook of Industrial Chemistry and Biotechnology (12th ed.). New York: Springer. ISBN 978-1-4614-4259-2. 
  13. ↑ "Archived copy". http://www.ingenia.org.uk/ingenia/issues/issue45/harris.pdf. 
  14. ↑ Nordin, Margareta (2001). Basic Biomechanics of the Musculoskeletal System. New York: Lippincott Williams & Wilkins. pp. 401–419. ISBN 978-0-683-30247-9. 
  15. ↑ "Mpausa - Methacrylates & Why They Are Important". http://www.mpausa.org/about-methacrylates2/. 
  16. ↑ https://www.gluegun.com/blogs/adhesive-reviews/a-user-s-guide-to-methyl-methacrylate-adhesives?srsltid=AfmBOopaSh9a1qxeR8MBqqUb4J46mMZ2GFMTDHyQW1A2m775Ef_n5deL
  17. ↑ "Methyl methacrylate". NIOSH Pocket Guide to Chemical Hazards. Centers for Disease Control and Prevention. https://www.cdc.gov/niosh/npg/npgd0426.html. 
  18. ↑ "ICSC 0300 - Methyl methacrylate". International Chemical Safety Cards. UN International Labour Organization and World Health Organization. https://www.ilo.org/dyn/icsc/showcard.display?p_lang=en&p_card_id=0300&p_version=2. 
  19. ↑ "Concise International Chemical Assessment Document 4 : METHYL METHACRYLATE". https://www.who.int/ipcs/publications/cicad/en/cicad04.pdf. 
  20. ↑ "Archived copy". http://www.cdph.ca.gov/programs/hesis/Documents/mma.pdf. 



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