Pyrolysis of Lactic Acid Derivatives. Preparation of Allyl and Methallyl Acrylates<sup>1</sup>

Fisher, C. H.; Rehberg, C. E.; Smith, Lee T.

doi:10.1021/ja01245a010

Cited by 13 publications

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“…Methacrylic acid was distilled under reduced pressure before use. Allyl methacrylate (AMA) was synthesized via the procedure reported by Fisher et al;36 the fraction distilling at 42.5–44.0 °C and 17 mmHg was collected. Benzyl dithiobenzoate (BDB) and cumyl dithiobenzoate (CDB) were synthesized with a reported procedure 37.…”

Section: Methodsmentioning

confidence: 99%

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Reversible addition–fragmentation chain transfer mediated radical polymerization of asymmetrical divinyl monomers targeting hyperbranched vinyl polymers

Lin

Liu

et al. 2006

J. Polym. Sci. A Polym. Chem.

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Reversible addition-fragmentation chain transfer (RAFT) mediated radical polymerizations of allyl methacrylate and undecenyl methacrylate, compounds containing two types of vinyl groups with different reactivities, were investigated to provide hyperbranched polymers. The RAFT agent benzyl dithiobenzoate was demonstrated to be an appropriate chain-transfer agent to inhibit crosslinking and obtain polymers with moderate-to-high conversions. The polymerization of allyl methacrylate led to a polymer without branches but with five-or six-membered rings. However, poly(undecenyl methacrylate) showed an indication of branching rather than intramolecular cycles. The hyperbranched structure of poly(undecenyl methacrylate) was confirmed by a combination of 1 H, 13 C, 1 H-1 H correlation spectroscopy, and distortionless enhancement by polarization transfer 135 NMR spectra. The branching topology of the polymers was controlled by the variation of the reaction temperature, chain-transfer-agent concentration, and monomer conversion. The significantly lower inherent viscosities of the resulting polymers, compared with those of linear analogues, demonstrated their compact structure. V V C 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: [26][27][28][29][30][31][32][33][34][35][36][37][38][39][40] 2007

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Section: Methodsmentioning

confidence: 99%

“…UMA was prepared with the modified published procedure 36. 10‐Undecen‐1‐ol (51 g, 0.3 mol), methacrylic acid (103 g, 1.2 mol), p ‐toluenesulfonic acid (1.0 g) as a catalyst, hydroquinone (3.0 g) as an inhibitor, and 30 mL of benzene were charged into a 500‐mL flask equipped with a moisture trap and a water condenser.…”

Section: Methodsmentioning

confidence: 99%

Reversible addition–fragmentation chain transfer mediated radical polymerization of asymmetrical divinyl monomers targeting hyperbranched vinyl polymers

Lin

Liu

et al. 2006

J. Polym. Sci. A Polym. Chem.

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“…Hydrolysis (22,26,36) of the polymers in the presence of a catalyst or at elevated temperatures is rapid. • Methyl (2,23), ethyl (7,10), isopropyl (8), isoamyl (10), glyceryl (10), allyl (20), and benzyl (37) lactates have been prepared by treating polylactic acid with the appropriate alcohol. Wislicenus (44) prepared lactamide and ammonium lactate by treating polylactic acid with ammonia.…”

Section: Previous Investigationsmentioning

confidence: 99%

Lactic Acid Condensation Polymers

Filachione¹,

Fisher²

1944

Ind. Eng. Chem.

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223 S = channel slope t = time U = mean velocity in z direction v = turbulent velocity component perpendicular to direction of w2 = mean square value of e, Y2 = mean square value of transverse spread of diffusing matter 2 = distance downstream from point a t which diffusing matter mean flow -is injected xo = scale of turbulence defined by Rdx e = kinematic eddy viscosity p = fluid density T = unit shear in fluid LITERATURE CITED (1) Dryden, H. L., IND. ENQ. ONDENSATION products or polymers of C lactic acid are important because: (a) They occur in all aqueous solutions of lactic acid containing approximately 18% lactic acid or more. (b) They are promising chemical intermediates. (c) The condensa-The preparation, properties, and reactions of condensation polymers of lactic acid are reviewed; batch and continuous methods for converting lactic acid into its condensation polymers are described. Removal of water during the dehydration or self-esterification of lactic acid is facilitated by relatively high temperature, reduced pressure, sulfuric acid or similar esterification catalyst, and an entraining agent, such as benzene or toluene. The resulting condensation polymers, which react readily with methanol, are useful for making methyl lactate. tion polymers of intermediate molecular weight can be used as such or after slight alteration as plasticizers. (d) The condensation products of higher molecular weight can be converted into useful plastics by condensation with certain vegetable oils, glycols, and other chemicals. (e) They are excellent for storing and transporting lactic acid in a highly concentrated condition; the completely polymerized linear product (I) and lactide (11) are equivalent to 125% lactic acid:Our interest in the production and properties of polymerized lactic acid was created largely by finding that the linear condensation polymers constitute an excellent starting point for making methyl lactate (19). When methyl lactate is formed by the interaction of polylactic acid and methanol, probably alcoholysis as well as esterification is involved, and only small quantities of water are formed in the reaction. Absence of water is advantageous because methyl lactate is readily hydrolyzed during distillation when appreciable quantities of water are present. Moreover, methyl lactate and water distill as an azeotropic mixture. The present paper summarizes earlier information on polylactic acid, much of which (3, 6) has not been readily available and describes both batch and continuous methods for dehydrating or polymerizing lactic acid. PREVIOUS INVESTIGATIONSAlthou h the reported findings o f previous workers are not in complete agreement, aqueous lactic acid solutions and dehydrated lactic acid appear to consist mainly of "free lactic acid:' (monomeric a-hydrox onic .acid), water, an^^^^^^ condensation or self-esterification products, such as lactyl lactic acid and lactyl lactyl lactic acid, 111: HOCH(CHs)COOCH(CHs)COOCH(CHs)COOH (111)These three components occur in various proportions, the extreme limits b...

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“…With the demonstration that compounds 2a and 2b could be prepared in very high yields using low levels of Pd and easily isolated by distillation, we sought to investigate whether the pyrolysis of the propionyloxy esters would also result in alkyl acrylate formation as in the case of the acetoxy analogues. − Compound 2a was added dropwise with a flow of CO 2 gas into a vertical quartz tube heated to 550–560 °C and packed with 1 g of silicon carbide supported on quartz wool (see SI for full details). After complete addition over the course of ∼50 min, a crude oil was obtained, the 1 H NMR spectrum of which was relatively clean and was shown to be composed mostly of a mixture of methyl acrylate, propionic acid, and propionic anhydride (Figure ).…”

Section: Resultsmentioning

confidence: 99%

“…However, these routes generally suffer from limited conversions and yields. − Early work from the 1930s and 1940s also showed that pyrolysis of alkyl 2-acetoxypropanoate derivatives, which can be obtained from alkyl lactates directly by acetylation, gives the corresponding alkyl acrylates in varying yields with acetic acid as the coproduct in an atom economic process (Scheme ). − The nature of the alkyl (R) group of the starting lactate was shown to significantly affect the yield of the acrylate ester obtained. , Newer work in this area has focused on the nickel catalyzed acetylation of lactide (the cyclic dimer of lactic acid) with acetic acid to give 2-acetoxypropionic acid, which can be subsequently pyrolyzed to give acrylic acid or converted to the methyl ester for production of methyl acrylate . This route is attractive in that it gives high yields of acrylic acid or methyl acrylate from lactide, and utilizes readily available nickel(II) nitrate and nickel(II) acetate as the acetylation catalysts, but requires somewhat harsh conditions.…”

Section: Introductionmentioning

confidence: 99%

Bioderived Acrylates from Alkyl Lactates via Pd-Catalyzed Hydroesterification

Yee

Tonks

2018

ACS Sustainable Chem. Eng.

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The conversion of methyl and ethyl lactate to their corresponding alkyl 2-(propionyloxy)propanoate esters was achieved by Pd catalyzed hydroesterificative coupling with carbon monoxide (CO) and ethylene (C2H4) at moderate temperatures and CO/C2H4 pressures. A screening of reaction conditions showed that the reaction could be carried out at low loadings of catalyst, which was generated in situ from inexpensive and commercially available reagents. High conversions and product yields were obtained in a variety of solvents and even under neat conditions. Product analysis identified transesterification to be the primary competing reaction, which could be mitigated by changing solvents, as well as minimizing the amount of excess acid present in solution. Pyrolysis of methyl and ethyl 2-(propionyloxy)propanoate transformed these esters into their respective acrylates suitable for subsequent polymerization, along with propionic acid as a valuable coproduct.

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Pyrolysis of Lactic Acid Derivatives. Preparation of Allyl and Methallyl Acrylates¹

Cited by 13 publications

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Reversible addition–fragmentation chain transfer mediated radical polymerization of asymmetrical divinyl monomers targeting hyperbranched vinyl polymers

Reversible addition–fragmentation chain transfer mediated radical polymerization of asymmetrical divinyl monomers targeting hyperbranched vinyl polymers

Lactic Acid Condensation Polymers

Bioderived Acrylates from Alkyl Lactates via Pd-Catalyzed Hydroesterification

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Pyrolysis of Lactic Acid Derivatives. Preparation of Allyl and Methallyl Acrylates1

Cited by 13 publications

References 0 publications

Reversible addition–fragmentation chain transfer mediated radical polymerization of asymmetrical divinyl monomers targeting hyperbranched vinyl polymers

Reversible addition–fragmentation chain transfer mediated radical polymerization of asymmetrical divinyl monomers targeting hyperbranched vinyl polymers

Lactic Acid Condensation Polymers

Bioderived Acrylates from Alkyl Lactates via Pd-Catalyzed Hydroesterification

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Pyrolysis of Lactic Acid Derivatives. Preparation of Allyl and Methallyl Acrylates¹