(12) United States Patent (10) Patent No.: US 6,215,018 B1 Miller Et Al
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USOO6215O18B1 (12) United States Patent (10) Patent No.: US 6,215,018 B1 Miller et al. (45) Date of Patent: Apr. 10, 2001 (54) ACRYLATE MONOMER PREPARATION 5,554,785 9/1996 Trapasso et al. .................... 560/201 USING ALKALI METALALKOXDES AS 5,606,103 2/1997 Trapasso et al. ................. 560/217 ESTER INTERCHANGE CATALYSTS AND 6,008.404 * 12/1999 Miller. RNERIT POLYMERIZATION FOREIGN PATENT DOCUMENTS 1933536 1/1971 (DE). (75) Inventors: Timothy M. Miller, East Brunswick; 2455717 5/1975 (DE). Narayanan Pondicherry, North 1274,837 5/1972 (GB). Brunswick; Louis E. Trapass0, West OTHER PUBLICATIONS Long Branch; Aaron van de Sande, Ocean, all of NJ (US) Journal of Polymer Science vol. 449-460, Hsieh et al. (73) Assignee: Ciba Specialty Chemicals * cited by examiner Corporation, Tarrytown, NY (US) Primary Examiner-Gary Geist (*) Notice: Subject to any disclaimer,- 0 the term of this ASSistant Examiner Robert W. Deemie patent is extended or adjusted under 35 (74) Attorney, Agent, or Firm-David R. Crichton U.S.C. 154(b) by 0 days. (57) ABSTRACT (21) Appl. No.: 09/416,586 The present invention relates to a process to prepare alkyl (meth) acrylate esters from corresponding alkyl/ (22) Filed: Oct. 12, 1999 methacrylate esters using an alkali metal alkoxide as an ester interchange catalyst to produce an alkyl (meth)acrylate ester Related U.S. Application Data OOC product C (62) Division of application No. 09/132,607, filed on Aug. 11, C 1998. (60) Provisional application No. 60/655.449, filed on Aug. 11, 1997. H.C=C-C-O-in-R,2u (51) Int. Cl." ................................................. CO1C 67/02 R (52) U.S. Cl. .............................................................. 560/217 4 (58) Field of Search ............................................... 560/217 The present invention further relates to the use of bromide (56) References Cited and iodide Salts as free radical polymerization inhibitors. U.S. PATENT DOCUMENTS The present invention further relates to the use of a nonin a terfering alcohol or polyol that prevents anionic polymer 4,056,580 11/1977 Lochmann et al............ 526/174 ization reactions of reactant ester B and/or alkyl (meth) 4,139,690 2/1979 Toriqoe et al. ...................... 526/174 acrylate product C. The present invention further relates to 4,672,105 : 6/1987 Schlosser. a process for inhibiting polymerization of (meth)acrylates 37. s SR al 526/174 being Synthesized in a transesterification or ester-ester inter 5,037,912 s/1991 Patterson et al... C2 change reaction system 5,424,420 6/1995 Hasenhuettlet al. ... 536/115 5,498,751 3/1996 Trapasso et al. .................... 560/217 15 Claims, No Drawings US 6,215,018 B1 1 2 ACRYLATE MONOMER PREPARATION and the camphene is a highly undesirable (because of its USING ALKALI METALALKOXDES AS odor) impurity in the product. There is an obvious need for ESTER INTERCHANGE CATALYSTS AND a new reaction Scheme which avoids the complications of an BROMIDE SALT POLYMERIZATION equilibrium reaction which cannot be driven to high con INHIBITORS version and an offensive impurity. Another approach to preparing isobornyl methacrylate involves transesterifica tion of isoborneol with methyl methacrylate; however, This is a divisional of application Ser. No. 09/132,607, isoborneol is an extremely high melting “cakey' Solid that is filed on Aug. 11, 1998, which claims the benefit under 35 difficult to handle on an industrial Scale. U.S.C. 119(e) of U.S. Provisional Application No. 60/655, A desirable methacrylate monomer is glycerol 449 filed Aug. 11, 1997. trimethacrylate, which is a trifunctional monomer having a low mass alcohol and a short distance between methacrylate SUMMARY OF THE INVENTION moieties. Due to Steric congestion Surrounding the Second The present invention relates to a process to prepare alkyl ary alcohol and its ease of elimination, industrial Syntheses (meth) acrylate esters from corresponding alkyl/ of glycerol trimethacrylate have been impractical using methacrylate esters using an alkali metal alkoxide as an ester 15 conventional reaction Sequences. interchange catalyst. Lithium methoxide or lithium Typical polymerization inhibitors are phenolic com t-butoxide, for example, catalyzes rapid formation of meth pounds Such as hydroquinone, 4-methoxyphenol, acrylate esters, Such as isobornyl methacrylate, hexyl pyrogallol, or hindered phenolics Such as butylated hydroxy methacrylate, and glycerol trimethacrylate, from their toluene and its derivatives. The oxygen in air Serves as the acetate esters in high yields with high Selectivity. The initial radical chain Stopper in these reactions Since it reacts present invention further relates to the use of polymerization at diffusion controlled rates with carbon centered radicals inhibitors, Li Br, MgBr and bromide salts of related metals which propagate chains in free radical polymerizations. The or counterions. Bromide Salts are useful as proceSS poly oxygen combines with the carbon centered radical to pro merization inhibitors in the preparation of methacrylate or duce a much longer lived peroxy radical. The peroxy radical 25 oxidizes a phenolic inhibitor and chain reactions are halted. acrylate esters from alcohols by transesterification or meth Other classes of inhibitors include metal ions such as Cu(II), acrylate esters from alkyl acetates by ester interchange. The aromatic nitro compounds, nitrous oxide, nitroxyl bromide Salts disclosed herein can be used to prevent compounds, aromatic amines, and aromatic heterocycles polymerization of the starting methyl (meth)acrylate or other such as phenothiazine (PTZ). Some of these require air to lower esters of (meth)acrylic acid in the reactor or distilla function effectively and others do not. Some have great tion column. utility for Some classes of monomers and others are not BACKGROUND OF THE INVENTION particularly useful for that class. The utility of Some proceSS inhibitors for a given class of monomers is even found to Methacrylate or acrylate monomers are generally made by depend upon the reaction conditions being used for their direct esterification of an alcohol or polyol with methacrylic 35 preparation. For instance, phenolic inhibitorS Such as hyd acid or acrylic acid, or by transesterification of an alcohol or roquinone are particularly useful for preparation of (meth) polyol with a lower ester of (meth)acrylic acid Such as acrylate esters by acid catalyzed direct esterification. Hyd methyl methacrylate or ethyl acrylate. In Such a process, a roquinone is a poor inhibitor for base catalyzed reactor is charged with the alcohol along with the desired transesterifications because it rapidly oxidizes under basic (meth)acrylate reactant and a Suitable catalyst. For instance, 40 conditions in the presence of air yielding dark reactions dodecanol is converted into dodecyl methacrylate with mixtures. methacrylic acid and methane Sulfonic acid. The reaction Polymerization inhibitors generally must be removed or mixture is heated and the water produced as a byproduct in diminished Substantially in concentration before the product the process is removed as its azeotrope with a hydrocarbon can be sold or polymerized by the end user. The high levels Solvent Such as heptane. In the case of transesterification, an 45 of inhibitor required to prevent polymerization during manu alcohol and methyl acrylate are heated in the presence of a facture prevent effective polymerization. In the case of tetraalkyl titanate, for instance, and the reaction is driven by Volatile monomers, Such as allyl methacrylate, removal of the byproduct, methanol. These reactions are dimethylaminoethylmethacrylate, hexyl acrylate, or methyl widely practiced in industry using a large variety of Specific acrylate, polymerization inhibitors can be removed via frac catalysts, reaction conditions and equipment optimized for 50 tional distillation. Most inhibitors have significantly higher the particular monomers being manufactured. Ester inter boiling points than distillable monomers and Separation can change reactions are also well-known, particularly for the be obtained. On the other hand, polymerization inhibitors randomization of fats and oils. The use of alkali metal cannot be removed from involatile monomerS Such as iso alkoxides is known for ester interchange reactions for fats decyl acrylate, lauryl methacrylate, Stearyl methacrylate, and oils. See also U.S. Pat. No. 5,424,420, which discloses 55 trimethylolpropane triacrylate and the like by distillation. a method for preparing Saccharide polyesters by transesteri Here, polymerization inhibitors must be removed via wash fication using an alkali metal alkoxide. ing for example by removing a phenolic inhibitor with Isobornyl methacrylate is a common monomer having aqueous Sodium hydroxide. In Some cases it is undesirable utility because of the high glass transition temperature of its to remove inhibitors via Washing because of yield losses, (co)polymers. It is conventionally prepared by acid cata 60 miscibility, process complexity, or the desire for waste lyzed addition of methacrylic acid to camphene. This reac minimization. In other cases, low volatility of the monomer tion proceeds, in the presence of an appropriate catalyst, makes it difficult to remove low levels of a powerful rapidly and cleanly but to low conversion because it is an inhibitor such as PTZ by distillation. Manufacturers of equilibrium reaction which cannot be driven by removal of monomers are always interested in inhibitors which permit a product. Thus, the