9011-14-7

Basic information

• Product Name: POLY(METHYL METHACRYLATE)
• Synonyms: METHYL METHACRYLATE POLYMER;METHYL METHACRYLATE, POLYMERIZED;METHYL METHACRYLATE RESIN;METHACRYLIC ACID METHYL ESTER POLYMER;LUCITE;POLY(METHYL METHACRYLATE-CO-ETHYL ACRYLATE);POLY(METHYL METHACRYLATE), ISOTACTIC;POLY(METHYL METHACRYLATE)
• CAS NO: 9011-14-7
• Molecular Formula: C15H24O6X2
• Molecular Weight: 300.35
• EINECS: 201-297-1
• Product Categories: Polymers;Acrylics;Contact Printing;Dielectric Materials;Hydrophobic Polymers;Materials Science;Methacrylate Polymers;Micro/NanoElectronics;Microcontact Printing;Organic and Printed Electronics;Organic Field Effect Transistor (OFET) Materials;PMMA-Based Resins;Polymer Science;Self Assembly &Stamps for Nanoprint Lithography &
• Mol File: 9011-14-7.mol
• Article Data: 178

Chemical Properties

• Melting Point: 150 °C
• Boiling Point: 108 °C
• Flash Point: 250 °C
• Appearance: White/powder
• Density: 1.188 g/mL at 25 °C
• Refractive Index: n20/D 1.49
• Storage Temp.: 2-8°C
• Solubility: alcohols and aliphatic hydrocarbons: insoluble
• Water Solubility: Soluble in tetrahydrofuran, toluene, cyclohexanone, ethyl acetate and chloroform. Insoluble in water, alcohols and aliphatic hyd
• Stability: Stable. Combustible. Incompatible with strong oxidizing agents.
• CAS DataBase Reference: POLY(METHYL METHACRYLATE)(CAS DataBase Reference)
• NIST Chemistry Reference: POLY(METHYL METHACRYLATE)(9011-14-7)
• EPA Substance Registry System: POLY(METHYL METHACRYLATE)(9011-14-7)

Safety Data

• Hazard Codes: Xn
• Statements: 20/22
• Safety Statements: 36-24/25-22
• WGK Germany: 3
• RTECS: TR0400000
• TSCA: Yes
• Hazardous Substances Data: 9011-14-7(Hazardous Substances Data)

Usage

Description

Poly(methyl methacrylate), commonly known as PMMA, is a versatile acrylic polymer derived from the monomer methyl methacrylate. It is known for its transparency, durability, and ease of processing, making it a popular material in various industries.

Uses

Used in Plastics Industry:
PMMA is used as a key component in the production of Carbonate-olefin based copolymer for molded plastics, offering a combination of strength, clarity, and workability.
Used in Analytical Chemistry:
PMMA serves as a reference suspension polymer for the analysis of its composition by gas chromatography method, providing a reliable standard for quality control and research purposes.
Used in Biomedical Applications:
In the biomedical field, PMMA/HA (Hydroxyapatite) composites are utilized for applications such as dentistry, orthopedic retainers, and bone replacement due to their biocompatibility and strength. Additionally, PMMA has been employed as a substrate for graphene growth, a material with promising properties for various applications.
Used in Nanotechnology:
PMMA-based nanocomposites, such as PMMA-titania hybrid optical thin films, PMMA/polystryrene/clay nanocomposites, and PMMA/polyurethane/carbon black nanocomposites for methanol fuel cells, are being developed to enhance the properties of PMMA and expand its range of applications in various industries.

Production method

PMMA can be obtained from its monomer using different techniques of polymerization. The monomer undergoes polymerization using the common methods of free radical and anionic initiations by bulk, solution, suspension, and emulsion techniques. [15] Following the discovery of a new technique of polymerization by Krzysztof Matyjaszewski in 1995[16] called Atom Transfer Radical Polymerization (ATRP), Matyjaszewski et al. successfully polymerized the monomer of methyl methacrylate (MMA) to produce PMMA as a living polymer with 80% conversion, poly-dispersity as low as 1.1, and an Mn of 20,000 in a few hours.[17]

Physicochemical properties

PMMA is one of the amorphous polymers that belong to the acrylate family. It is a clear, colorless polymer with a glass transition temperature range of 100 degree to 130 degree, and a density of 1.20 g/cm3 at room temperature. This polymer melts at 130 degree, with a water absorptivity of 0.3%, moisture absorption at equilibrium of 0.3 to 0.33%, and a linear shrinkage mold of 0.003 to 0.0065 cm/cm[18-20]. PMMA is among the polymers that have high resistance to sunshine exposure because it has a small variation under the effect of UV-radiation. It has very good thermal stability, and is known to withstand temperatures as high as 100 degree and as low as 70 degree. It also possesses very good optical properties, with a refractive index of 1.490, and a good degree of compatibility with human tissue.[18, 19] PMMA is an organic polymer, and its solubility is expected to be governed by “like-dissolve-like,” with polarity playing a major role. PMMA shows little deviation, as its solubility is more complex, starting with swelling in the solvent and the subsequent formation of a very soft layer on its surface. This is then followed by diffusion of the solvent into the whole polymer before it gives a homogenous solution with the solvent. This is the reason why PMMA takes a few minutes before it is dissolved completely, even if it is in its best solvent. PMMA hydrolyzed completely with sulfuric acid (H2SO4) to become poly (methacrylic acid) (PMAA). Hydrochloric acid and hydro-iodic acid are capable of hydrolyzing PMMA, but at a slow rate when compared to sulfuric acid[21]. PMMA has a predominantly elemental composition of carbon and hydrogen. Therefore, it is liable to undergo an exothermic combustion reaction to yield gaseous products (CO2, CO, H2O,) and energy like any other hydrocarbon. The thermal decomposition of PMMA has been extensively studied in the absence of oxygen. The decomposition temperature varies, depending on the approach used in the synthesis of the polymer. Radically polymerized PMMA containing terminal C-C bonds decompose at a temperature of 220 degree with simple mechanisms of monomer repeat units bond scission and C-C bond random scission [18].

References

Malcom, P.S. Polymer Chemistry: An Introduction. 3rd ed.; Oxford University Press: NY, pp 167–176, 256–276. Henri, L. Thermohygroelastic Properties of Polymethylmethacrylate; 2007, Netherlands. pp. 11–13. Demir, M. M.; Memesa, M.; Castignolles, P.; Wegner, G. Macromolecular Rapid Communications. 2006, 27 (10), 763–770. Hashim, H.; Adam, N. I.; Zaki, N.H.M.; Mahmud, Z.S.; Said, C.M.S.; Yahya, M.Z.A.; Ali, A.M.M. Conference on Science and Social Research 2010 (CSSR 2010), Kuala Lumpur, Malaysia, 485–488. Henry, A.C.; Tutt, T.J.; Galloway, M.; Davidson, Y.Y.; McWhorter, C.S.; Soper, S.A.; McCarley, R.L. Analytical Chemistry 2000, 72(21), 5331–5337. Lee, L.H.; Chen, W.C. Chem. Mater. 2001, 15, 1137–1142. Shah, J. J.; Geist, J.; Locascio, L. E.; Gaitan, M.; Rao, M. V.; Vreeland, W. N. “Surface modification of poly(methyl methacrylate) for improved adsorption of wall coating polymers for microchip electrophoresis”, Electrophoresis 2006, 27(19), 3788–3796. Adhikari, B.; Majumdar, S. “Polymers in sensor applications”, Progress in Polymer Science 2004, 29(7), 699–766. Isha, A.; Yusof, N.A.; Ahmad, M.; Suhendra, D.; Yunus, W.M.Z.W.; Zainal, Z. Sensors and Actuators B: Chemical. 2006, 114(1), 344–349. Kost, J.; Langer, R. “Responsive polymeric delivery systems”, Advanced Drug Delivery Reviews. 2012, 64, 327–341. Beruto, D.T.; Botter, R.; Fini, M. Biomaterials. 2002, 23(12), 2509–2517. Shi, M.; Kretlow, J.D.; Spicer, P.P.; Tabata, Y.; Demian, N.; Wong, M.E.; Kasper, F.K.; Mikos, A.G. Journal of Controlled Release 2011, 152(1), 196–205. Mishra, S.; Sen, G. International Journal of Biological Macromolecules. 2011, 48(4), 688–694. Wang, M.; Pramoda, K.P.; Hong, S. Polymer 2005, 46, 11510–11516. George, O. Principles of Polymerization, 4th ed.; Wiley: NJ, 2004, pp 198–235. Wang, J.-S.; Matyjaszewski, K. Journal of the American Chemical Society. 1995, 117(20), 5614–5615. Grimaud, T.; Matyjaszewski, K. Macromolecules. 1997, 30(7), 2216–2218. Charles, A.H.; Edward, M.P. Plastics Materials and Processes, in Concise Encyclopedia; Wiley: NJ, 2003, pp. 42–44. Van Krevelen, D.W.; Nijenhuis, K. T. Properties of Polymers; Elsevier: Amsterdam, 2000, pp. 106, 322. Charles, A.H. Handbook of Plastics Processes; Wiley: NJ, 2006, pp. 1–7. Ishitake, K.; Satoh, K.; Kamigaito, M.; Okamoto, Y. Polymer Chemistry. 2012, 3(7), 1750–1757. Zuhair, J.; Abdul Amer, J.K.A.; Sura Fahim, A. “Chitosan/PMMA bioblend for drugs release applications”, International Journal of Engineering and Technology 2014, 4(5), 318–324. Tai, Y.; Wang, L.; Gao, J.; Amer, W.A.; Ding, W.; Yu, H. Journal of Colloid and Interface Science. 2011, 360(2), 731–738. Camara, R.M.; Portela, R.; Gutierrez-Martin, F.; Sanchez B. Global NEST Journal 2014, 6(3), 525–535. Haik, M.Y.; Ayesh, A.I.; Abdulrehman, T.; Haik, Y. Materials Letters. 2014, 124(0): 67–72. Hallinan, D.T.; Balsara, N.P. Polymer Electrolytes, in Annual Review of Materials Research, Vol 43, D.R. Clarke, Ed.; 2013, pp. 503–525 Shen, J.; Li, Z.; Cheng, R.; Luo, Q.; Luo, Y.; Chen, Y.; Chen, X.; Sun, Z.; Huang, S. ACS Applied Materials & Interfaces 2014, 6(20), 17454–17462. Perween, M.; Parmar, D.B.; Bhadu, G.R.; Srivastava, D.N. “Polymer-graphite composite: a versatile use and throw plastic chip electrode”, Analyst 2014, 139(22), 5919–5926.

Preparation

The polymerization of methyl methacrylate:is readily accomplished by bulk, solution, suspension and emulsion techniques. Of these methods, bulk and suspension polymerization are mainly used for the production of the homopolymer.(a) Bulk polymerization Techniques which involve a combination of bulk polymerization and casting are extensively used in the manufacture of poly(methyl methacrylate) sheet. In most processes, the first step is the preparation of a partially polymerized material. Typically, monomer is stirred with benzoyl peroxide (0.5%) at 90°C for about 10 minutes to give a syrup which is then cooled to room temperature. Colourant, plasticizer and ultraviolet absorber, if required, are added at this point. At this stage the degree of conversion of monomer to polymer is about 20%; the use of such a syrup reduces shrinkage in the casting cell and also lessens leakage from the cell. The syrup is then poured into a casting cell, consisting of two glass plates separated by a rubber gasket. The plates are held together by spring-loaded clamps so that the plates continuously move together in response to the shrinkage of approximately 20% which occurs on conversion of monomer to polymer. The filled cell is then passed through a heating tunnel wherein the temperature is maintained at 40°C for 15 hours and then 95°C for 1 hour. The sheet is then cooled and removed from the cell. With castings of thickness greater than about 2 cm, the exothermic reaction may result in local temperatures above the boiling point of the monomer (100Se) and bubbles may form. In such cases, polymerization may be carried out under pressure so that the boiling point of the monomer is raised. Rod is also manufactured by casting. In one process, syrup is contained in vertical aluminium tubes which are very slowly lowered into a bath at 40°C. As the lowest portion of syrup polymerizes it contracts and the syrup above moves downwards. In this way a homogeneous rod, free from voids, is obtained. Dentures are normally made from a polymer-monomer dough in a plaster mould. Bulk polymerization carried out in the preparation of sheet, as described above, results in polymer of very high average molecular weight (≈106).(b) Suspension polymerizution Suspension polymerization of methyl methacrylate is used mainly for the production of injection moulding and extrusion grades of polymer. Suspension polymer is also used in the preparation of polymer-monomer doughs for dentures. Polymerization is carried out batch-wise in a stirred reactor, jacketed for heating and cooling; the reactor is capable of withstanding a pressure of 0.3--0.4 MPa (3-4 atmospheres).Reaction is carried out under nitrogen. Typically, the mixture is initially heated to about 80°C but the exothermic reaction causes the temperature to rise to about 120°C, with accompanying increase in pressure. Polymerization is rapid and is complete in about 1 hour. The suspension is cooled and acidified with sulphuric acid to remove the suspending agent. The beads of polymer are then filtered off, washed and dried in air at about 80°C. The dried beads may be used for moulding without further treatment or they may be compounded with additives (e.g. colourants), extruded and granulated. Suspension polymerized poly(methyl methacrylate) normally has an average molecular weight of about 60000.

Safety Profile

Questionable carcinogen with experimental tumorigenic data by implant route. When heated to decomposition it emits acrid smoke and irritating fumes. Used as the main constituent of acrylic sheet, moldmg, and extrusion powders.

InChI:InChI=1/C5H7O2/c1-4(2)5(6)7-3/h1H,2-3H3

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Relevant articles and documents

Esterification or Thioesterification of Carboxylic Acids with Alcohols or Thiols Using Amphipathic Monolith-SO3H Resin

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 CATALYST AND A PROCESS FOR THE PRODUCTION OF ETHYLENICALLY UNSATURATED CARBOXYLIC ACIDS OR ESTERS

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.

The effect of the bimetallic Pd-Pb structures on direct oxidative esterification of methacrolein with methanol

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.