TECHNICAL BULLETIN MAGNESIUM METHYLATE MGME-8 Liquid Magnesium Methoxide (8% Solution) DESCRIPTION MGME-8 is a new liquid form of Magnesium Methylate (8% solution). Unlike solid Magnesium Methylate, MGME-8 combines the convenience of handling with hydroxide-free quality. As a solution in anhydrous methanol, MGME-8 brings the versatility of this unique catalyst in a solvent compatible to most applications. As a mild solvent soluble alkali, free of amines, MGME-8 is an ideal catalyst for anhydrous reactions where hydrolysis or dehydration potential exists. APPLICATIONS Transesterification Catalyst for Polyester, Acrylics, and Epoxies Catalyst for Alkoxylation Catalyst for Olefin and Vinyl Polymerizations Production of Overbased Lubricating Oils Mild source of Methoxy radicals for anionic polymerization reactions Enolization and condensation reactions of ketones and aldehydes Meerwein Poondorf reaction Methanolysis Production of solvent gels Drying agent for solvents BENEFITS Milder alkali than sodium or calcium alkoxides Solution form in Methanol is ready to use and safer than handling solids Hydroxide free for faster reactivity and higher yields Methanol carrier solvent is easier to remove than other systems and compatible with most applications Can be easily precipitated for improved removal No milling, grinding or pre-dissolving needed Effective at removing trace moisture from anhydrous systems or reactions TYPICAL PROPERTIES Appearance Clear water white. Slight hydroxide haze on storage or exposure to air. Assay 7.5 8.5% Specific Gravity 0.845 0.855 Flash Point (COC) 58 F Odor None Stability Readily hydrolyzes to form Mg(OH) 2 Addition of water to product will result in gel formation HEALTH & SAFETY PRECAUTIONS MGME-8 should be handled with the same precautions as any flammable liquid. Use in open areas away from flames or sparks and with grounding straps to prevent accidental static discharge. As a solution in methanol, care should be exercised to minimize inhalation of vapors, as methanol is a toxic chemical and should be regarded as a cumulative poison. USE ADEQUATE VENTILATION. Storage of MGME-8 should be restricted to areas with adequate heating but away from open flames. To protect from crystallization, keep stored between 40-80 o F. Because of the gradual absorption of moisture from the air and the subsequent formation of insoluble hydroxides, the recommended shelf life of MGME-8 is 6 months. Refer to Material Safety Data Sheet on MGME-8 for additional safety and health information. The MSDS is revised as new data becomes available. PACKAGING & AVAILABILITY MAGNESIUM METHYLATE MGME-8 is available in 5 gallon plastic pails with Reike pour spouts (36 lbs. net) and 55 gallon steel closed head non-returnable drums (380 lbs. net). 11/24/08 Supplying Specialty Thermosets Worldwide PAGE 1
APPLICATIONS REVIEW Transesterification Catalyst MGME-8 is an ideal transesterification catalyst capable of high yields while performing under mild reaction conditions. Under normal use, MGME-8 can minimize or eliminate undesireable side reactions like dehydration, polymerization or ring opening often found in other alkoxides. Well established successes have been documented in the following types of transesterification reactions: Ester Methyl acrylate and methacrylate Other alkyl acrylates Fatty methyl esters Methyl benzoate and phthalates Methoxy functional polymers Co-reactant Glycols Branched alcohols Caprolactone Glycerine Aliphatic amides Other monomeric and polymeric polyols Polyesters Production of polyester resins via transesterification of dicarboxylic esters and aliphatic polyols can be accomplished with MGME-8. These reactions conform to the general formula: nch 3 OOCRCOOCH 3 + nhr OH Mg(OCH 3 ) 2 HR OOCRCOOR H + nch 3 OH Where R can be any polyether, polyester or polycarbonate Since this route is carried out under anhydrous conditions to liberate methanol instead of water, reaction temperatures are lower and rates faster because methanol is more easily removed. Lower temperatures also result in fewer by-products, less discoloration and better control. Typical reaction conditions are 70-180 o C depending on the melting points of the two components and can be completed in 10-30 minutes as measured by evolution of methanol. Application levels of 0.05-0.20% MGME-8 (active) by weight of dicarboxylic acid ester are normal. Unlike other catalysts, magnesium methylate will not discolor the final product and will not produce undesirable by products typical of acid based catalysts. Polyesters produced via this route also have better tensile strength and improved heat stability. The spent magnesium methylate can be easily filtered from the resultant polyester and will aid in achieving the lowest possible moisture content. 11/24/08 Supplying Specialty Thermosets Worldwide PAGE 2
Olefins MGME-8 in conjunction with MgCl 2 and TiCl 4 is an effective high yield polymerization catalyst for Polyethylene. At molor ratios of 5-10:1 of TiCl 4 to MGME-8 (dry) and a corresponding molar ratio of 10-15:1 of MgCl 2 to TiCl 4, a high productivity catalyst system can be formed which is capable of increasing polymerization rates 3-5 times that of catalysts systems not containing magnesium methylate. Use of magnesium methylate can also be effective on production of compound catalysts free of chlorine for polypropylene production. Vinyl Similar improvements are also achievable in vinyl monomer polymerizations. Magnesium methylate is effective in increasing the rate of reaction of compound catalyst systems for vinyl polymerizations. Use of organic peroxides alone limit the ability to regulate polymerization speed and can often require higher temperatures to initiate polymerization with some peroxides. Compound systems based on organic peroxides, alkyl sulfates or phosphates, and MGME-8 can increase reaction rates at lower temperatures yielding products with improved thermal stability. Organic peroxide levels of.5-2.0% by weight of monomer are generally used. MGME-8 and alkyl sulfate levels are added at a slight excess on an active basis to the peroxide. OTHER APPLICATIONS Specialty Methoxides Metal oxides such as Aluminum, Barium or Strontium dissolved in methanol can be reacted with MGME-8 to produce the corresponding methylate, precipitating magnesium hydroxide. Unlike sodium methylate, magnesium methylate will produce an insoluble precipitate to facilitate removal. These methoxides have use in alkali metal mercaptide synthesis and catalytic coatings. DMT Recovery Depolymerization of polyester scrap through methanolysis of polyterephthalate resin scrap to yield high quality dimethyl terephthate (DMT). Methoxy Derivatives Production of dimethoxy alkanes with lower alkane chain alchohols from chloroalkanes. Magnesium methylate has been shown to be more effective than other alkoxides as a suitable acid scavenger eliminating problems of dehydrohalogenation common with stronger bases such as sodium hydroxide or methoxide. MGME-8 is also an economic source of Methoxy radicals for production of methoxy phenolic derivatives. The reaction produces magnesium hydroxide as a by-product which is easily filtered and yields methoxy phenolics in high yield without competing side reactions. 11/24/08 Supplying Specialty Thermosets Worldwide PAGE 3
Specialty Acrylic Esters Higher chain length methacyrlate esters are readily produced by reaction with the corresponding alcohol. MGME-8 concentrations of.2 -.5% (dry) are generally adequate. The reaction is stoichiometric and is driven to almost quantitative completion even at low temperatures by distillation of the methyl alcohol produced. Ex: Lauryl Acrylate from Lauryl alcohol and Methyl Acrylate Transesterification catalyzed by MGME-8 is also ideal to produce specialty esters from substituted derivatives where the substitution group would compete in direct esterification (eg. substituted alcohols, amines or halogens). Acrylamide For acrylamide production MGME-8 is ideally suited to reactions involving methyl acrylate (MA) or methyl methacrylate (MMA) and aliphatic amides. The reaction utilizes.5 -.7% MGME-8 (dry) based on MMA concentration and is quantitative yielding the corresponding methyl ester and acrylamide without hydrolysis by-products. Other methyl ester transesterifications are also possible with MGME-8. Reaction conditions and yields will vary with the co-reactants. Alkoxylation Catalyst MGME-8 is a preferred catalyst for alkoxylation of detergent grade alcohols. As a soluble magnesium source, MGME-8 can be used in ethoxylation and propoxylation of fatty alcohols. Typically ethoxylation of fatty alcohols is catalyzed by Lewis acids or alkali bases. However, Lewis acids tend to produce high quantities of polyalkylene glycols and leave undesirable byproducts. Furthermore, they are not inductive to EO adducts > 3. As disclosed in recent patents, addition of MGME-8 (2-5 mole% dry) to a fatty alcohol reaction mixture which has been first seeded with 7-10% of a 2 mole adduct of the fatty alkoxylate, can yield substantially quantitative conversion with minimal (<.5%) polyethylene glycol formation. Olefin and Vinyl Polymerization Polymerization of olefins and vinyl monomers are accelerated by Magnesium Methylate as part of compound catalyst systems. By working with liquid MGME-8, the selected metal salts used can be uniformly treated with magnesium methylate to provide more uniform coverage and particle size with lower fines levels than possible with grinding. 11/24/08 Supplying Specialty Thermosets Worldwide PAGE 4
Condensations Aldehyde condensations and enolization reactions are made practical with liquid MGME-8 in catalytic quantities. Examples are Tischenko condensations of aldehydes: 2R-CHO Mg(OCH 3 ) 2 RCH 2 CO 2 R Meerwein Ponndorf reactions: RCOR + RCH(OH) R Mg(OCH 3 ) 2 R CH(OH) R + RCOR DISCLAIMER The information contained herein is believed to be reliable, but no representations, guarantees or warranties of any kind are made as to its accuracy, suitability for particular applications or the results to be obtained there from. The information is based on laboratory work with small-scale equipment and does not necessarily indicate end product performance. Because of the variations in methods, conditions, and equipment used commercially in processing these materials, no warranties or guarantees are made as to the suitability of the products for the applications disclosed. Full-scale testing and end product performance are the responsibility of the user. CVC Thermoset Specialties shall not be liable for and the customer assumes all risk and liability of any use or handling of any material beyond CVC s direct control. THE SELLER MAKES NO WARRANTIES, EXPRESS OR IMPLIED, INCLUDING, BUT NOT LIMITED TO, THE IMPLIED WARRANTIES OR MERCHANTABILITY AND FITNESS FOR A PARTICULAR PURPOSE. Nothing contained herein is to be considered permission, recommendation, nor as an inducement to practice any patented invention without permission of the patent owner. IN NO EVENT SHALL SELLER BE LIABLE FOR ANY INCIDENTAL, CONSEQUENTIAL OR SPECIAL DAMAGES. 844 N. Lenola Road/Moorestown, NJ 08057 An Emerald Performance Materials Company Copyright 2006 Emerald Performance Materials LLC. 6/2006 11/24/08 Supplying Specialty Thermosets Worldwide PAGE 5