Methacrylates from /-butyl alcohol

Because of the problems with disposal of the bisulfate waste and the handling of HCN, much research has been devoted to alternative processes. The new processes range from using new feedstocks such as isobutylene / t-butyl alcohol, ethylene, isobutane or methylacetylene to techniques for recycling the HCN and / or ammonium bisulfate279 28°. In 1998 Asahi replaced 60,000 tonnes per year of MMA capacity based on direct oxidation of isobutylene with a new process that also starts with isobutylene. However the new direct oxidative esterification (DOE) process makes MMA by the simultaneous oxidation and esterification of methacrolein, which eliminates the intermediate production of methacrylic acid298. 

Production of methyl methacrylate from tertiary butyl alcohol... 

BASF has recently patented a reactive azeotropic distillation process to produce esters from methacrylic acid and alcohols, involving a total of 3 columns. Although the patent example is for butyl methacrylate, they claim methyl methacrylate as well. 

Conversion of the phthalimide to the amine was confirmed by a peak at (5 3.2 ppm corresponding to the hydrogen adjacent to the amine group. The functionalization reaction was also monitored by MALDI-TOF MS. Characterization of the phthalimide-functionalized polymer confirmed the conversion of the bromide group. Characterization of the amine-functionalized polymer showed the presence of the desired product, but other side products were also observed. Upon hydrolysis of the phtha-limide-functionalized polymer, a transesterification reaction occurs converting the initiator moiety (ethyl-2-bromoisobuty-rate) from an ethyl ester to a t-butyl ester due to reaction with t-butyl alcohol. One drawback of this reaction is that the Gabriel reaction is only effective for primary alkyl halides and would not be useful for methyl methacrylates or methyl acrylates. 

Figure 13.6 Life cycle of polyfmethyl methacrylate) (PMMA)-containing products. MMA, Methyl methacrylate ACH, acetone cyanohydrin method TBA-DO, tertiary butyl alcohol (isobutylene) direct oxidation method TBA-DOE, tertiary butyl alcohol (isobutylene) direct oxidative esterification method C2, ethylene method TR, thermal recovery MR, material recycling. Modified from Kikuchi Y, Hirao M, Ookubo T Sasaki A. Design of recycling system for polyfmethyl methacrylate) (PMMA). Part 1 recycling scenario analysis. Int J Life Cycle Assess 20i4 i9(i) 120—9.

At one time it was felt that C4 oxidation technology would be the most probable basis for new methyl methacrylate production [14]. This technology would require isobutylene or f-butyl alcohol available as byproducts from ethylene production or from the Oxirane process (Scheme 2.5) used for the manufacture of propylene oxide. 

Chen et al. prepared fluorinated acrylate resin [55] by solution polymerization of a mixture of 2-(perfluoro-( 1,1 -iti>isopropyl)-2-propenyl)oxy-ethyl methacrylate (POMA), butyl acrylate (BA), methyl methacrylate (MMA), and methacrylic acid (MA) in the co-solvents of ethyl acetate, butyl alcohol, and toluene using AIBN as initiator. First, POMA was synthesized as the starting reactants from the intermediate perfluoro nonene and 2-HEMA. Consequently, a series of fluorinated acrylate resins was synthesized with the same solid content, whereas the fluorine content in mixed monomers was varied at 0%, 5%, 10%, 15%, 20%, and 25%. Films of the novel fluorinated acrylate resin were made by spreading the resin on a clean Petri dish followed by drying at room temperature. Scheme 6.13 shows the synthesis pathway of the fluorinated acrylate resin. 

Increa sing the bulkiness of the alkyl group from the esterifying alcohol in the ester also restricts the motion of backbone polymer chains past each other, as evidenced by an increase in the T within a series of isomers. In Table 1, note the increase in T of poly(isopropyl methacrylate) over the / -propyl ester and similar trends within the butyl series. The member of the butyl series with the bulkiest alcohol chain, poly(/-butyl methacrylate), has a T (107°C) almost identical to that of poly(methyl methacrylate) (Tg = 105° C), whereas the butyl isomer with the most flexible alcohol chain, poly( -butyl methaciylate), has a T of 20°C. Further increase in the rigidity and bulk of the side chain increases the T. An example is poly(isobomyl methacrylate)... 

Acrylic Esters. A procedure has been described for preparation of higher esters from methyl acrylate that illustrates the use of an acid catalyst together with the removal of one of the products by azeotropic distillation (112). Another procedure for the preparation of butyl acrylate, secondary alkyl acrylates, and hydroxyalkyl acrylates using -toluenesulfonic acid as a catalyst has been described (113). Alurninumisopropoxide catalyzes the reaction of amino alcohols with methyl acrylate and methyl methacrylate. A review of the synthesis of acryhc esters by transesterification is given in Reference 114 (see... 

PVC can be blended with numerous other polymers to give it better processability and impact resistance. For the manufacture of food contact materials the following polymerizates and/or polymer mixtures from polymers manufactured from the above mentioned starting materials can be used Chlorinated polyolefins blends of styrene and graft copolymers and mixtures of polystyrene with polymerisate blends butadiene-acrylonitrile-copolymer blends (hard rubber) blends of ethylene and propylene, butylene, vinyl ester, and unsaturated aliphatic acids as well as salts and esters plasticizerfrec blends of methacrylic acid esters and acrylic acid esters with monofunctional saturated alcohols (Ci-C18) as well as blends of the esters of methacrylic acid butadiene and styrene as well as polymer blends of acrylic acid butyl ester and vinylpyrrolidone polyurethane manufactured from 1,6-hexamethylene diisocyanate, 1.4-butandiol and aliphatic polyesters from adipic acid and glycols. 

It is a tertiary alcohol with the hydroxyl group flanked by two identical R (= butyl) groups. The chemists who wanted to make the compound knew that an ester would react twice with the same organolithium reagent, so they made it from this unsaturated ester (known as methyl methacrylate) and butyllithium. 

As seen from the previous examples, poly(methacrylic acid esters) generate a significant amount of monomer. Small amounts of compounds derived from two monomer or even three monomer units can be seen in some pyrograms (when the elution from the selected chromatographic column is feasible). However, the use of Py-GC/MS for polymer identification can be based mainly on the presence of the monomer. Some difficulty may arise in differentiating esters with isomeric alcohol component such as poly(n-butyl methacrylate) and poly(/so-butyl methacrylate), since 2-methyl-2-propenoic acid n-butyl ester and 2-methyl-2-propenoic acid 2-methylpropyl ester have very similar mass spectra. 

Polymer-grafted silica (SiO2) particles represent one of the most popular colloidal systems with tunable interactions. Ilie chains of choice were mainly polystyrene, poly(dimethyl siloxane), poly(butyl methacrylate), and n-octadecyl or stearyl alcohol. Chain grafting provided the means to tailor the colloidal particle behavior from hard to soft, as well as introduce attractions in a controlled way by varying the temperature or adding non-absorbing polymer depletant [44,95-112]. 

Muller and coworkers prepared disc-like polymer Janus particles from assembled films of the triblock copolymer SBM and, after hydrolysis of the ester groups into methacrylic acid units, used these as Pickering stabilizer in the soap-free emulsion polymerization of styrene and butyl acrylate [111]. Armes and coworkers described the synthesis of PMMA/siUca nanocomposite particles in aqueous alcoholic media using silica nanoparticles as stabilizer [112], extending this method to operate in water with a glycerol-modified silica sol [113, 114]. Sacanna showed that methacryloxypropyltrimethoxysilane [115] in the presence of nanosized silica led to spontaneous emulsification in water, which upon a two-step polymerization procedure afforded armored particles with an outer shell of PMMA [116]. Bon and coworkers demonstrated the preparation of armored hybrid polymer latex particles via emulsion polymerization of methyl methacrylate and ethyl methacrylate stabilized by unmodified silica nanoparticles (Ludox TM O) [117]. Performance of an additional conventional seeded emulsion polymerization step provided a straightforward route to more complex multilayered nanocomposite polymer colloids (see Fig. 14). 

Ettre and Varady used these techniques in the investigations of decomposition products of poly(vinyl alcohol), poly(n-butyl methacrylate), and nitrocellulose from 500 to 950 °C (cf. Section 4.2.1.1 and Table 4.15). 

The affect of variations in chemical structure of amines on the photo-initiating ability of 4- -propoxythio-xanthone was also investigated in photopolymerizations of n-butyl methacrylate and a commercial triacrylate resin in isopropyl alcohol solution. The conclusion from that study is that the activity is highly dependent on the ionization potential of the particular amine, the formation of a triplet exciplex and an electron transfer process. Analyses of chloroform extracts of the cured resin confirmed that the alkylamino radical is the initiating radical. ... 

Fig. 17.2 Transmission electron micrograph of polypyrrole particles of (a) 100 nm diameter, (b) 200 nm diameter, and (c) 300 nm diameter synthesized in aqueous media using a poly(vinyl alcohol) stabilizer, a poly(2-vinyl pyridine-co-Ai-butyl methacrylate) stabilizer, and a poly(ethylene oxide) stabilizer, respectively. Note the uniform spherical morphology. (Reproduced with permission from Ref. 28.1...

For economic reasons the dominant esters worldwide are butyl and 2-ethylhexyl acrylate. The 3M Company, the largest tape producer in the U.S., is reported to manufacture for captive consumption the ester of isooctyl alcohol derived from the 0X0 process. Other acrylate esters, such as decyl and isodecyl acrylate, and certain methacrylate esters, such as lauryl methacrylate, give rise to the requisite low-7 homopolymer but are currently too expensive for commercial consumption. Although a large... 

---