WO2015002746A2 - Biobased epoxidized fatty acid ester plasticizers - Google Patents

Biobased epoxidized fatty acid ester plasticizers Download PDF

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Publication number
WO2015002746A2
WO2015002746A2 PCT/US2014/043122 US2014043122W WO2015002746A2 WO 2015002746 A2 WO2015002746 A2 WO 2015002746A2 US 2014043122 W US2014043122 W US 2014043122W WO 2015002746 A2 WO2015002746 A2 WO 2015002746A2
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Prior art keywords
acid
alcohol
benzyl
reacting
biomass
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PCT/US2014/043122
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French (fr)
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WO2015002746A3 (en
Inventor
George F. Schaefer
John D. Bradshaw
Larry J. Baldwin
Ronald J. Raleigh
Brenda Hollo
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Ferro Corporation
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Priority to EP14820291.4A priority Critical patent/EP3016938A4/en
Publication of WO2015002746A2 publication Critical patent/WO2015002746A2/en
Publication of WO2015002746A3 publication Critical patent/WO2015002746A3/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
    • C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
    • C07C67/11—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond being mineral ester groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/12—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/006—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by oxidation

Definitions

  • the invention relates to plasticizers that are fully or partially sourced from renewable sources such as biomass, post-consumer waste streams and recycled plastics.
  • renewable sources such as biomass, post-consumer waste streams and recycled plastics.
  • the use of such plasticizers reduces the carbon footprint of processes that make various plastics.
  • Plasticizers are compounds or mixtures of compounds that are added to polymer resins to impart softness and flexibility. Most commercial plasticizers are sourced from fossil-based materials such as crude oil.
  • U.S. Patent 288,814 covers esters of tetrahydrofurfuryl alcohol including tetrahydrofurfuryl-9-octadecenoate (tetrahydrofurfuryloleate).
  • U.S. Patent 2,568,989 covers the use of tetrahydrofurfuryl-9-octadecenoate as a light stabilizer for alkyl diaryl phosphite plasticized PVC.
  • Plasticizers based on carbon from flora or fauna sources will provide improved sustainability and also reduce the amount of carbon dioxide being added to the atmosphere.
  • Flora and fauna derived raw materials that can be used to produce plasticizers include abietic acid, alkyl alcohols in general, butanol, butanediols, benzyl chloride, epoxidized glycerides, hexanediols, isosorbide, isobutanol, furoic acid, furfuryl alcohol, phthalic anhydride, phthalic acid, saturated fatty acids, succinic anhydride, succinic acid, tetrahydrofurfuryl alcohol, toluene, unsaturated fatty acids, and xylenes.
  • Esters of tetrahydrofurfuryl alcohol (THFA ), especially tetrahydrofurfuryl oleate, are used as primary and extender-type plasticizers.
  • the oleate ester is a very stable, light-colored plasticizer which improves the low temperature flexibility of vinyl products. It is also used as a carrier to incorporate stabilizers into vinyl resin formulations.”
  • plasticizers based on bioderived raw materials including those in the preceding paragraph can be accomplished using esterification techniques followed by
  • Plasticizers that can be made by esterification include benzyl alkyl phthalates, dialkyl phthalates, dialkyl succinates, benzyl alkyl succinate, dialkyl adipates, benzyl alkyl adipates, dialkyl 1,2-cyclohexanedicarboxylates, benzyl alkyl 1,2-cyclohexanedicarboxylates, tetrahydrofuryl fatty acid esters, tetrahydrofuryl unsaturated fatty acid esters, furoates of epoxidized diglycerides and diol furoates.
  • the above plasticizers made with bio derived raw materials constitute a significant improvement in sustainable industrial processes because the resource is completely renewable.
  • An embodiment of the invention is a method of making an epoxidized fatty acid ester comprising: (a) providing at least one alcohol selected from the group consisting of furfuryl alcohol, tetrahydroforfuryl alcohol, ethanol, butanol, benzyl alcohol, 2-ethylhexanol, 2- propylheptanol, C 3 - C 31 alcohols, (b) providing at least one fatty acid, (c) wherein at least one of the alcohol and the fatty acid is biomass sourced, (d) reacting the at least one alcohol with the at least one fatty acid in the presence of an alkoxide catalyst, to afford an esterified fatty acid, (e) combining the esterified ester with a natural unsaturated triglyceride, and (f) reacting the mixture of esterified fatty acid and natural unsaturated trigly
  • An embodiment of the invention is a method of making an epoxidized fatty acid ester comprising: (a) providing at least one alcohol selected from the group consisting of furfuryl alcohol, tetrahydrofivrfuryl alcohol, ethanol, butanol, benzyl alcohol, 2-ethylhexanol, 2- propylheptanol, C 3 - C 31 alcohols, (b) providing at least one fatty acid, (c) wherein at least one of the alcohol and the fatty acid is biomass sourced, (d) reacting the at least one alcohol with the at least one fatty acid in the presence of an alkoxide catalyst, to afford an esterified fatty acid, (d) reacting the esterified fatty acid with an oxidizer and an acid to form an epoxidized fatty acid ester.
  • at least one alcohol selected from the group consisting of furfuryl alcohol, tetrahydrofivrfuryl alcohol, ethanol, butanol, benzyl
  • Another embodiment of the invention is a method of making a plasticizer comprising (a) obtaining cyclohexane-l,2-dicarboxylic acid anhydride from a biomass source, (b) obtaining butanol from a biomass source, (c) obtaining benzyl chloride from a biomass source, (d) reacting the cyclohexane-l,2-dicarboxylic acid anhydride with the butanol, optionally in the presence of heat, to form 2-(butoxycarbonyl) cyclohexanecarboxylic acid, (d) reacting the 2- (butoxycarbonyl) cyclohexanecarboxylic acid with a Bronsted-Lowry base to form a conjugate pair, (e) reacting the conjugate pair, with benzyl chloride to form benzyl butyl cyclohexane 1, 2- dicarboxylate.
  • Another embodiment of the invention is a method of making a plasticizer comprising (a) obtaining cyclohexane- 1,2-dicarboxylic acid anhydride from a biomass source, (b) obtaining butanol from a biomass souixe, (c) obtaining benzyl chloride from a biomass source, (d) reacting the cyclohexane- 1,2-dicarboxylic acid anhydride with the butanol, optionally in the presence of heat, to form 2-(butoxycarbonyl) cyclohexanecarboxylic acid, (d) reacting the 2- (butoxycarbonyl) cyclohexanecarboxylic acid with N, N-diethylethanamine to form N-N- diemylethaminiuni 2-butoxycarbonyl cyclohexanecarboxylate, (e) reacting the N-N- diethylethaminium 2-butoxycarbonyl cyclohexanecarboxylate, with benzyl
  • An embodiment of the invention is a method of making a plasticizer comprising: (a) obtaining C4 to C e dicarboxylic acid anhydride from a biomass source, (b) obtaining a C3 to Cio alkyl alcohol from a biomass source, (c) obtaining benzyl chloride from a biomass source,(d) reacting the dicarboxylic acid anhydride with the alkyl alcohol, to form an alkoxycarbonyl carboxylic acid, (e) reacting the alkoxycarbonyl carboxylic acid with N, N- diethylethanamine to form N-N-diethylethaminium alkoxycarbonyl carboxylate, and (f) reacting the N-N-diethylethaminium alkoxycarbonyl alkylcarboxylate, with benzyl chloride to form benzyl alkyl dicarboxylate.
  • a C 4 to Cio dicarboxylic acid anhydride may be used from a
  • the invention further relates to processes of making plasticized thermoplastic polymers including the addition of any plasticizer herein to a thermoplastic polymer.
  • Figure 1 depicts various conversion pathways from biomass sources to plasticizers or chemical products.
  • the compounds of the invention are used to soften thermoplastic polymer resins that would otherwise be brittle and inappropriate for many applications. Plasticizers improve flexibility and tensile strength in such resins.
  • Bioderived sources of starting materials for esterification reactions to make the plasticizers of interest can come from a number of sources.
  • Ethanol and butanol can be derived from biomass through fermentation of sugars or starch.
  • Butanol can also be derived from biobased starch or sugars which are used to feed Clostridia that produce butanols.
  • Butanediol can be produced from biobased starches and sugars which are used to feed Enterobacter cloacae bacteria that produce 2,3-butanediol.
  • Biomass can be used as a source for producing carbon monoxide and hydrogen gases which mixture is also Icnown as Syngas. The production of many chemicals including alkyl alcohols, and aromatics is currently accomplished from Syngas and appropriate catalyst systems.
  • An embodiment of the invention is a method of making an epoxidized fatty acid ester comprising: (a) providing at least one alcohol selected from the group consisting of furfuryl alcohol, teh'ahydrofurfuryl alcohol, ethanol, butanol, benzyl alcohol, 2-ethylhexanol, 2- propylheptanol, C 3 - C 3 i alcohols, (b) providing at least one fatty acid, (c) wherein at least one of the alcohol and the fatty acid is biomass sourced, (d) reacting the at least one alcohol with the at least one fatty acid in the presence of an alkoxide catalyst, to afford an esterified fatty acid, (d) reacting the esterified fatty acid with an oxidizer and an acid to form an epoxidized fatty acid ester.
  • at least one alcohol selected from the group consisting of furfuryl alcohol, teh'ahydrofurfuryl alcohol, ethanol, butanol, benz
  • the at least one alcohol may be furfuryl alcohol or tetrahydrofurfuryl alcohol, and wherein the at least one fatty acid is selected from the group consisting of myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, linolenic acid, arachidonic acid, eicopentaenoic acic, erucic acid, docosohexanoic acid, a group of fatty acids sourced from soybeans, a group of fatty acids sourced from linseeds, and combinations thereof.
  • the at least one fatty acid is selected from the group consisting of myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, linolenic
  • the alkoxide catalyst may be sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, or combinations thereof.
  • the fatty acid may be linoleic acid or generally soybean oil. If the biomass carbon source is soybean oil, then the at least one fatty acid is 5-10 wt% alpha-linolenic acid, 45-55 wt% linolenic acid, 20-25 wt% oleic acid, 2-7 wt% stearic acid and 5-15 wt% palmitic acid.
  • the alcohol is tetrahydrofurfuryl alcohol.
  • An embodiment of the invention is a plastic mass or article including any plasticizer disclosed herein or made by a process disclosed herein.
  • Hemicelluloses in oat hulls, corn cobs, wheat bran, sugar cane bagasse, sawdust, or wood chips when heated with steam in an anaerobic digester with aqueous sulfuric acid will yield D- xylose and L-arabinose (pentosans) that further dehydrate to give furfural. Approximately 10% of the plant matter can be converted to furfural. Quaker Oats was at one time a major producer of furfural. It is estimated that 250,000 to 450,000 tons of furfural are produced annually, principally by China and the Sasol Company.
  • Nickel catalysts and alternative molybdenum doped cobalt catalysts to make tetraJaydrofurfuryl alcohol are described in the literature. Copper-clrromite catalyst is used to make furfuryl alcohol.
  • Epoxidized Tetrahydrofurfuiyl-9-octadecenoate (below) is a new molecule with 100% bio-derived carbon. Synthesis of this molecule could be approached in two manners: 1) epoxidation of the parent tetrahydrofurfuryl-9-ocatcedecenoate, or 2) epoxidation of high-oleic soybean oil or other natural or genetically modified seed oil followed by transesterifi cation.
  • Epoxidized Tetrahydrofurfurylsoyate Transesterification of epoxidized soybean oil (ESO) with tetrahydrofurfuryl alcohol can be catalyzed by sodium methoxide or a derived sodium tetxahydrorarfuryloxide. All (100%) of the carbon in this molecule is bio-derived. Ferro Corporation makes ESO, and has the capability to hydrogenate furfuryl aldehyde to furfuryl alcohol. Further hydrogenation or hydrogenation of furfuryl aldehyde with a different catalyst would yield tetrahydrofurfuryl alcohol. Glycerin is a byproduct that is removed by gravity separation. Steam distillation is useful in removing tetrahydrofurfuryl alcohol, aldehydes and other byproducts. Epoxidized tetrahydrofurfuryl soyate is shown below.
  • R may be benzyl or furyl alcohols such as fixrfuryl, tetrahydro furfuryl, 1 -(2 -furyl) ethanol, l(tetrahydrofuran-2-yl) ethanol, below,
  • Plasticizers based on bio-derived raw materials such as benzyl succinates, benzyl phthalates, benzyl cyclohexane-l,2-carboxylates, epoxidized furyl fatty acid esters and phosphate esters are contemplated herein.
  • Benzyl succinates such as benzyl butyl succinate, benzyl isobutyl succinate, benzyl pentyl succinate, benzyl 2-methylbutyl succinate, benzyl 3-methylbutyl succinate, benzyl hexyl succinate, benzyl heptyl succinate, benzyl 2-ethylhexyl succinate, benzyl n-octyl succinate, benzyl isononyl succinate, benzyl nonyl succinate, benzyl 2-propylheptyl succinate, benzyl decyl succinate.
  • Benzyl Phthalates such as benzyl butyl phthalate, benzyl isobutyl phthalate, benzyl pentyl phthalate, benzyl 2-methylbutyl phthalate, benzyl 3-methylbutyl phthalate, benzyl hexyl phthalate, benzyl heptyl phthalate, benzyl texanyl phthalate, benzyl 2-ethylhexyl phthalate, benzyl n-octyl phthalate, benzyl isononyl phthalate, benzyl nonyl phthalate, benzyl 2- propylheptyl phthalate, benzyl decyl phthalate.
  • Benzyl cyclohexane-l,2-dicarboxylate include but are not limited to benzyl butyl cyclohexane- 1,2-carboxylate, benzyl isobutyl cycIohexane-l,2-carboxylate, benzyl pentyl cyclohexane-l,2-carboxylate, benzyl 2-methylbutyl cyclohexane-l,2-carboxylate, benzyl 3- methylbutyl cyclohexane- 1,2-carboxylate, benzyl hexyl cyclohexane- 1,2-carboxylate, benzyl heptyl cyclohexane- i ,2-carboxylate, benzyl 2-ethylhexyl cyclohexane-l,2-carboxylate, benzyl n- octyl cyclohexane-
  • Benzoates include but are not limited to butyl benzoate, isobutyl benzoate, pentyl benzoate, 2-methylbutyl benzoate, 3-methylbutyl benzoate, hexyl benzoate, heptyl benzoate, texanyl benzoate, 2-ethylhexyl benzoate, n-octyl benzoate, 2,2,4-trimethylpentane-l,3-diyl dibenzoate, isononyl benzoate, nonyl benzoate, 2-propylheptyl benzoate, decyl benzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate.
  • Epoxidized fatty acid esters of benzyl alcohol and furyl alcohols which include but are not limited to furfuryl alcohol, tetrahydrofurfuryl alcohol, l-(2-furyl)ethanol, l-(2- tetrahydrofuran-2-yl) ethanol.
  • Epoxidized fatty acid esters include the bio-produced oils but are not limited to the following; soy oil, canola oil, castor oil, citrus seed oil, coconut oil, cod liver oil, corn oil, cottonseed oil, cuphea oil, linseed oil, oat oil, olive oil, palm oil, palm kernel oil, lard, peanut oil, rapeseed oil, rice bran oil, safflower oil, safflower high oleic oil, sesame oil, soybean oil, sunflower oil, sunflower high oleic oil, tung oil with furfuryl alcohol,
  • Phosphate esters include but are not limited to dibutylphenyl phosphate, di-(2- ethylhexyl)phenyl phosphate, tri-(2-ethylhexyl) phosphate, triburyl phosphate, tri-isobutyl phosphate, tri-(2-butoxyethyl) phosphate, 2-ethylhexyl diphenyl phosphate, n-octyl diphenyl phosphate, isononyl diphenyl phosphate, nonyl diphenyl phosphate, 2-propylheptyl diphenyl phosphate, tri-(tertiary butylphenyl phosphate, tertiaiy-butylphenyl diphenyl phosphate, di- (tertiary-butylphenyl)phenyl phosphate, triphenyl phosphate.
  • Epoxidized fatty acid methyl esters are contemplated herein.
  • dicarboxylates, and fatty acid esters is derived from biomass through the treatment of bio-mass to obtain syngas.
  • the syngas is then used to prepare toluene directly or by converting syngas to methanol.
  • the methanol is reacted with ZSM-5 catalyst to produce a benzene, toluene and all three isomers of xylene, BTX (benzene, toluene, xylene) mixture.
  • the BTX mixture is distilled to give commercial toluene.
  • the toluene is converted to benzyl chloride and the benzyl chloride can be used directly in esterification with dicarboxylic acid anhydrides or the benzyl chloride can be easily converted to benzyl alcohol and then the esterification of the carboxylic acids to the esters which are common to the listed plasticizer except for the phosphate esters.
  • Bio-derived aliphatic alcohols for use in succinates, phthalates, cyclohexane-1,2- dicarboxylates, benzoates, and phosphates are made by first forming syngas from biomass followed by formation of methanol.
  • the methanol is converted to olefins using a Zeolite catalyst.
  • the olefins can be oligomerized and metathesized into a range from 2 carbon 30 carbons by a process such as SHOP.
  • the olefins can de distilled apart to give either a mixture or a single olefin.
  • the olefin or mixtures of olefins with carbon number 2 to 15 are converted to aldehydes with 1 carbon more than the olefin by hydroformylation which utilizes syngas and a catalyst.
  • the aldehyde can be either hydrogenated to alcohol or oxidized to the corresponding acid.
  • bio-mass derived aliphatic linear and branched aicohois with carbon number ranging from 3 to 16 are available to use in the general esterification, transesterification and esterification utilizing benzyl chloride to form alkyl benzyl diester reactions to form the plasticizers.
  • Succinic acid utilized in making succinic anhydride is being produced commercially from sugars and starches that are biomass derived.
  • the phenyl moiety used in making phosphate esters is derived from biomass through the treatment of bio-mass to obtain syngas. The syngas is then used to prepare aromatics. Benzene is formed in a BTX process from aromatics formed from the syngas. Cumene is formed from benzene and propylene. The propylene is formed from the biomass and syngas. Phenol is formed from cumene and acetone in the cumene peroxidation process.
  • succinates include dibenzyl succinate, w hich is obtained from the reaction of benzyl chloride and the disodium salt of succinic acid. Such a process would not require production of benzyl alcohol, and would not require converting the bio-succinic acid to succinic anhydride, as shown below.
  • Asymmetric succinates might also be made via phase transfer catalysis but would require reaction of an aliphatic alcohol with succinic anhydride prior to the phase transfer catalysis reaction with benzyl chloride. Tetrahydromrfuryl alcohol and a variety of other alcohols would be useful in the reaction scheme below.
  • Sebacic acid is a derivative of castor oil, and is biobased.
  • An embodiment of the invention is a method of making a plasticizer comprising: (a) obtaining C 4 to C 16 dicarboxylic acid anhydride from a biomass source, (b) obtaining a C 3 to Qo alkyl alcohol from a biomass source, (c) obtaining benzyl chloride from a biomass source, (d) reacting the dicarboxylic acid anhydride with the alkyl alcohol, to form an alkoxycarbonyl carboxylic acid, (e) reacting the alkoxycarbonyl carboxylic acid with N, N-diethylethanamine to form N-N-diethylethaminium the alkoxycarbonyl carboxylate, and (f) reacting the N-N- diemyletharninium alkoxycarbonyl alkylcarboxylate, with benzyl chloride to form benzyl alkyl dicarboxylate.
  • the dicarboxylic acid anhydride is suitably a dialkyl acid anhydride.
  • the dicarboxylic acid anhydride may be an aryl di-acid anhydride, such as succinic anhydride, phthalic anhydride, or adipic anhydride.
  • An embodiment of the invention is a method of making a plasticizer comprising: (a) obtaining sebacic acid anhydride from a biomass source, (b) obtaining a C 3 to C 10 alkyl alcohol from a biomass source, (c) obtaining benzyl chloride from a biomass source, (d) reacting the sebacic acid anhydride with the alkyl alcohol, to form an alkoxysebacic acid, (e) reacting the alkoxysebacic acid with N, N-diethylethanamine to form N-N-diethylethaminium alkoxysebacic carboxylate, and (f) reacting the N-N-diethylethaminium alkoxysebacic carboxylate, with benzyl chloride to form benzyl alkyl sebacate.
  • Another embodiment of the invention involves provision of benzyl alcohol for other process steps, the benzyl alcohol, provided by a process comprising, (a) treating biomass to obtain lignocellulose, (b) treating lignocellulose to obtain syngas, (c) treating syngas to obtain toluene, with an optional intermediate step of obtaining methanol, (d) treating methanol with a zeolite catalyst to produce a BTX mixture, (e) distilling the BTX mixture to give toluene, (f) converting the toluene to benzyl chloride, and (g) converting the benzyl chloride to benzyl alcohol.
  • An embodiment of the invention is a plastic mass or plastic article including any plasticizer made by any method disclosed herein.
  • Phase Transfer Catalysis (PTC) synthesis of benzyl acetate and benzyl benzoate is suitable in the invention. Broadly, all dibasic acids with 4 to 10 carbon atoms is envisioned, especially succinic acid, a C4 dibasic acid.
  • the catalysts used are potassium iodide or sodium bromide (for halogen exchange) and quaternary ammonium salts (for phase transfer). In some instances, the quaternary ammonium salts can be produced in situ from benzyl chloride and tributylamine.
  • Aqueous solution of the sodium salt of the acid and KI or NaBr can be combined with a toluene solution of the tertiary amine. Upon heating the reaction a desired set temperature, benzyl chloride is added. Yields as high as 96% benzyl n-butyl phthalate (using KI), 99% benzyl benzoate (using NaBr), and 96% benzyl acetate (using KI) can be obtained.
  • any organic or inorganic base may be used, such as Bronsted-Lowry bases, including triaUcylamines.
  • Suitable Bronsted-Lowry bases include ammonium ion and primary, secondary and tertiary ammonium ions and their salts.
  • Quaternary ammonium hydroxides such as tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, tripropyl amine, tributyl amine, benzyl dimethyl amine, dibenzyl methyl amine, and benzyl diethyl amine.
  • trialkyl amines as well as amines having a benzyl group and two alkyl groups or two benzyl groups and an alkyl group are useful.
  • the alkyl groups in the aforementioned examples independently have 1-20 carbon atoms, preferably 1-10 carbon atoms, more preferably 1-8 carbon atoms.
  • additives include antioxidants, such as primary and secondary antioxidants, which may be included separately or together.
  • any plasticizer disclosed herein directly or made by any method herein may be accompanied by at least one primary antioxidant and/or at least one secondary antioxidant.
  • Antioxidants can be divided in two basic classifications: primary and secondary antioxidants.
  • Primary antioxidants interrupt oxidation degradation by tying up the free radicals. They react rapidly with peroxy radicals to break growing chains.
  • Secondary antioxidants destroy the unstable hydroperoxides that function as sources of free radicals during oxidative degradation. They react with hydroperoxides to yield nonreactive products. Thus, secondary antioxidants are also known as hydroperoxide decomposers.
  • the two major groupings among the primary antioxidants are hindered phenolics and aromatic amines. Primary antioxidants function by donating their reactive hydrogen to the peroxy free radicals so that the propagation of subsequent free radicals does not occur.
  • antioxidants for polymer protection are phenolics. These products generally resist staining or discoloration. However, they may form quinoid structures upon oxidation, which leads to yellowing.
  • Amines normally arylamines, may be more effective than phenolic, but most are staining and discoloring and lack FDA approval for use in contact with food. Amines are commonly used in the rubber industry, but they are also used in applications such as wire and cable formulations and in polyurethance polyols.
  • Secondary antioxidants are used in conjunction with primary antioxidants to provide added stability to the polymer and ether containing compounds. They function by decomposing hydroperoxides to form nonreactive products. Typical secondary antioxidant compounds contain sulfur or phosphorous. The more popular secondary antioxidants are thioesters (thiodipropinonic acid derivatives and polythiodipropionates) and
  • Secondary Phosphite Antioxidants useful in the present invention include tris (2,4-di-tert- butylphenyl) phosphite, distearyl pentaerythritol diphosphate, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite; poly(dipropylene glycol) phenyl phosphite, 2-ethylhexyl diphenyl phosphite, triisodecyl phosphite, phenyl diisodecyl phosphite, diphenyl isodecyl phosphite, triphenyl phosphite, and tris(nonylphenyl)phosphite. Most preferred is trilauryl phosphite.
  • Antioxidant Blends Every stabilizer has a specific temperature range in which it develops its optimum properties. For this reason, antioxidant system (stabilizer packages) combining two or more materials are often used. Such blends are commercially available as a single additive. The most effective mixture will combine a free radical inhibitor (primary antioxidant) with a peroxide decomposer (secondary antioxidant). The free radical inhibitor retards the initiation of reaction chains, but some hydroperoxide is nevertheless formed. A peroxide decomposer available to react with the hydroperoxide prevents it from decomposing with free radicals. This feature can provide a measure of safety when a hydroperoxide, which is known to decompose violently, is safely decomposed using a peroxide decomposer.

Abstract

Compounds useful as plasticizers and the synthesis thereof are disclosed. In general, the invention includes process of esterifying biobased alcohols to make biobased ester plasticizers and the plasticizers made by such processes.

Description

BIOBASED EPOXJDIZED FATTY ACID ESTER PLASTICIZERS
BACKGROUND OF THE INVENTION
1. Field of Invention
[0001] The invention relates to plasticizers that are fully or partially sourced from renewable sources such as biomass, post-consumer waste streams and recycled plastics. The use of such plasticizers reduces the carbon footprint of processes that make various plastics.
2. Description of Related Art
[0002] Plasticizers are compounds or mixtures of compounds that are added to polymer resins to impart softness and flexibility. Most commercial plasticizers are sourced from fossil-based materials such as crude oil.
[0003] U.S. Patent 288,814 (R. H. Van Schaack, Jr., 1928) covers esters of tetrahydrofurfuryl alcohol including tetrahydrofurfuryl-9-octadecenoate (tetrahydrofurfuryloleate). U.S. Patent 2,568,989 (Monsanto, Cowell, 1951) covers the use of tetrahydrofurfuryl-9-octadecenoate as a light stabilizer for alkyl diaryl phosphite plasticized PVC. In 1965 Emery was manufacturing Plastolein 9250 (CAS RN 5420-17-7), which is tetrahydrofurfuryl-9-octadecenoate, and it was disclosed as a plasticizer in U.S. 3,219,064.
[0004] It would be useful in the plastics and plasticizers industries to provide biobased plasticizers to thereby reduce the carbon footprint of industrial processes.
SUMMARY
[0005] Plasticizers based on carbon from flora or fauna sources will provide improved sustainability and also reduce the amount of carbon dioxide being added to the atmosphere. Flora and fauna derived raw materials that can be used to produce plasticizers include abietic acid, alkyl alcohols in general, butanol, butanediols, benzyl chloride, epoxidized glycerides, hexanediols, isosorbide, isobutanol, furoic acid, furfuryl alcohol, phthalic anhydride, phthalic acid, saturated fatty acids, succinic anhydride, succinic acid, tetrahydrofurfuryl alcohol, toluene, unsaturated fatty acids, and xylenes. [0006] Esters of tetrahydrofurfuryl alcohol (THFA ), especially tetrahydrofurfuryl oleate, are used as primary and extender-type plasticizers. The oleate ester is a very stable, light-colored plasticizer which improves the low temperature flexibility of vinyl products. It is also used as a carrier to incorporate stabilizers into vinyl resin formulations."
Figure imgf000004_0001
2-furanyl Tetrahydrofurfuryl-9-octadecenoate 3-furanyl Tetrahydrofurfuryl-9-octadecenoate
CAS No. 5420-17-7 CAS No. 150-81-2
[0007] The inventors herein note that 100% of tetrahydromrfuryl-9-octadecenoate is bio-derived. The compounds have an inactive US FDA Drug Master File, suggesting this molecule is innocuous or possibly GRAS. 3-furanyl Tetrahydrofurfuryl-9-octadecenoate, CASRN 150-81-2. is registered on the December 2011 TSCA inventory and on REACH, where EINECS No. 205- 772-4 is on the list of Pre-Registered Substances as of March 2009, with a registration date of 30 November 2010. 2-furanyl Tetrahydrofirrfuryl-9-octadecenoate, CASRN 5420-17-7 was preregistered on REACH, where EINECS No. 226-532-5 is on the list of Pre-Registered
Substances as of March 2009, with a registration date of 30 November 2010 The established synthetic route both of these compounds is acid catalysis. The compound(s) is/are calculated to have a boiling point of 460°C, a density of 0.927 g/cmJ, and a freezing point of 173.5°C.
[0008] The production of plasticizers based on bioderived raw materials including those in the preceding paragraph can be accomplished using esterification techniques followed by
purification. Plasticizers that can be made by esterification include benzyl alkyl phthalates, dialkyl phthalates, dialkyl succinates, benzyl alkyl succinate, dialkyl adipates, benzyl alkyl adipates, dialkyl 1,2-cyclohexanedicarboxylates, benzyl alkyl 1,2-cyclohexanedicarboxylates, tetrahydrofuryl fatty acid esters, tetrahydrofuryl unsaturated fatty acid esters, furoates of epoxidized diglycerides and diol furoates. The above plasticizers made with bio derived raw materials constitute a significant improvement in sustainable industrial processes because the resource is completely renewable. These plasticizers made with bio-derived raw materials would also constitute a significant reduction in manmade carbon dioxide released into the biosphere. [0009] An embodiment of the invention is a method of making an epoxidized fatty acid ester comprising: (a) providing at least one alcohol selected from the group consisting of furfuryl alcohol, tetrahydroforfuryl alcohol, ethanol, butanol, benzyl alcohol, 2-ethylhexanol, 2- propylheptanol, C3- C31 alcohols, (b) providing at least one fatty acid, (c) wherein at least one of the alcohol and the fatty acid is biomass sourced, (d) reacting the at least one alcohol with the at least one fatty acid in the presence of an alkoxide catalyst, to afford an esterified fatty acid, (e) combining the esterified ester with a natural unsaturated triglyceride, and (f) reacting the mixture of esterified fatty acid and natural unsaturated triglyceride with an oxidizer and an acid to form an epoxidized fatty acid ester and epoxidized fatty acid triglyceride mixture.
[0010] An embodiment of the invention is a method of making an epoxidized fatty acid ester comprising: (a) providing at least one alcohol selected from the group consisting of furfuryl alcohol, tetrahydrofivrfuryl alcohol, ethanol, butanol, benzyl alcohol, 2-ethylhexanol, 2- propylheptanol, C3- C31 alcohols, (b) providing at least one fatty acid, (c) wherein at least one of the alcohol and the fatty acid is biomass sourced, (d) reacting the at least one alcohol with the at least one fatty acid in the presence of an alkoxide catalyst, to afford an esterified fatty acid, (d) reacting the esterified fatty acid with an oxidizer and an acid to form an epoxidized fatty acid ester.
[0011] Another embodiment of the invention is a method of making a plasticizer comprising (a) obtaining cyclohexane-l,2-dicarboxylic acid anhydride from a biomass source, (b) obtaining butanol from a biomass source, (c) obtaining benzyl chloride from a biomass source, (d) reacting the cyclohexane-l,2-dicarboxylic acid anhydride with the butanol, optionally in the presence of heat, to form 2-(butoxycarbonyl) cyclohexanecarboxylic acid, (d) reacting the 2- (butoxycarbonyl) cyclohexanecarboxylic acid with a Bronsted-Lowry base to form a conjugate pair, (e) reacting the conjugate pair, with benzyl chloride to form benzyl butyl cyclohexane 1, 2- dicarboxylate.
[0012] Another embodiment of the invention is a method of making a plasticizer comprising (a) obtaining cyclohexane- 1,2-dicarboxylic acid anhydride from a biomass source, (b) obtaining butanol from a biomass souixe, (c) obtaining benzyl chloride from a biomass source, (d) reacting the cyclohexane- 1,2-dicarboxylic acid anhydride with the butanol, optionally in the presence of heat, to form 2-(butoxycarbonyl) cyclohexanecarboxylic acid, (d) reacting the 2- (butoxycarbonyl) cyclohexanecarboxylic acid with N, N-diethylethanamine to form N-N- diemylethaminiuni 2-butoxycarbonyl cyclohexanecarboxylate, (e) reacting the N-N- diethylethaminium 2-butoxycarbonyl cyclohexanecarboxylate, with benzyl chloride to form benzyl butyl cyclohexane 1, 2-dicarboxylate.
[0013] An embodiment of the invention is a method of making a plasticizer comprising: (a) obtaining C4 to C e dicarboxylic acid anhydride from a biomass source, (b) obtaining a C3 to Cio alkyl alcohol from a biomass source, (c) obtaining benzyl chloride from a biomass source,(d) reacting the dicarboxylic acid anhydride with the alkyl alcohol, to form an alkoxycarbonyl carboxylic acid, (e) reacting the alkoxycarbonyl carboxylic acid with N, N- diethylethanamine to form N-N-diethylethaminium alkoxycarbonyl carboxylate, and (f) reacting the N-N-diethylethaminium alkoxycarbonyl alkylcarboxylate, with benzyl chloride to form benzyl alkyl dicarboxylate. In a preferred embodiment, a C4 to Cio dicarboxylic acid anhydride may be used from a biomass source.
[0014] The invention further relates to processes of making plasticized thermoplastic polymers including the addition of any plasticizer herein to a thermoplastic polymer.
[0015] The foregoing and other features of the invention are hereinafter more fully described and particularly pointed out in the claims, the following description setting forth in detail certain illustrative embodiments of the invention, these being indicative, however, of but a few of the various ways in which the principles of the invention may be employed.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Figure 1 depicts various conversion pathways from biomass sources to plasticizers or chemical products.
DETAILED DESCRIPTION OF THE INVENTION
[0017] The compounds of the invention are used to soften thermoplastic polymer resins that would otherwise be brittle and inappropriate for many applications. Plasticizers improve flexibility and tensile strength in such resins.
[0018] Bioderived sources of starting materials for esterification reactions to make the plasticizers of interest can come from a number of sources. Ethanol and butanol can be derived from biomass through fermentation of sugars or starch. Butanol can also be derived from biobased starch or sugars which are used to feed Clostridia that produce butanols. Butanediol can be produced from biobased starches and sugars which are used to feed Enterobacter cloacae bacteria that produce 2,3-butanediol. Succinic acid and derivatives butanediol, tetrahydrofuran and gamma-butyrolactone from biomass by fermentation as described in US 8,246,792, incorporated herein by reference. Biomass can be used as a source for producing carbon monoxide and hydrogen gases which mixture is also Icnown as Syngas. The production of many chemicals including alkyl alcohols, and aromatics is currently accomplished from Syngas and appropriate catalyst systems.
[0019] An embodiment of the invention is a method of making an epoxidized fatty acid ester comprising: (a) providing at least one alcohol selected from the group consisting of furfuryl alcohol, teh'ahydrofurfuryl alcohol, ethanol, butanol, benzyl alcohol, 2-ethylhexanol, 2- propylheptanol, C3- C3i alcohols, (b) providing at least one fatty acid, (c) wherein at least one of the alcohol and the fatty acid is biomass sourced, (d) reacting the at least one alcohol with the at least one fatty acid in the presence of an alkoxide catalyst, to afford an esterified fatty acid, (d) reacting the esterified fatty acid with an oxidizer and an acid to form an epoxidized fatty acid ester.
[0020] The at least one alcohol may be furfuryl alcohol or tetrahydrofurfuryl alcohol, and wherein the at least one fatty acid is selected from the group consisting of myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, linolenic acid, arachidonic acid, eicopentaenoic acic, erucic acid, docosohexanoic acid, a group of fatty acids sourced from soybeans, a group of fatty acids sourced from linseeds, and combinations thereof.
[0021] The alkoxide catalyst may be sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, or combinations thereof.
[0022] The fatty acid may be linoleic acid or generally soybean oil. If the biomass carbon source is soybean oil, then the at least one fatty acid is 5-10 wt% alpha-linolenic acid, 45-55 wt% linolenic acid, 20-25 wt% oleic acid, 2-7 wt% stearic acid and 5-15 wt% palmitic acid. In a preferred embodiment, the alcohol is tetrahydrofurfuryl alcohol.
[0023] An embodiment of the invention is a plastic mass or article including any plasticizer disclosed herein or made by a process disclosed herein. [0024] Hemicelluloses in oat hulls, corn cobs, wheat bran, sugar cane bagasse, sawdust, or wood chips when heated with steam in an anaerobic digester with aqueous sulfuric acid will yield D- xylose and L-arabinose (pentosans) that further dehydrate to give furfural. Approximately 10% of the plant matter can be converted to furfural. Quaker Oats was at one time a major producer of furfural. It is estimated that 250,000 to 450,000 tons of furfural are produced annually, principally by China and the Sasol Company. International Furan Chemicals B.V. in the Dominican Republic produces roughly 35,000 tons per year furfural from sugar cane bagasse. Nickel catalysts and alternative molybdenum doped cobalt catalysts to make tetraJaydrofurfuryl alcohol are described in the literature. Copper-clrromite catalyst is used to make furfuryl alcohol.
Hemicelluloses
H Δ
Figure imgf000008_0001
D-Xylose
l-Arabinose
- 3 H20
Figure imgf000008_0002
Furfural Furfuryl Alcohol Tetrahydrofurfuryl Alcohol
Furfural Production and Derivatization Schemes
[0025] Epoxidized Tetrahydrofurfuiyl-9-octadecenoate (below) is a new molecule with 100% bio-derived carbon. Synthesis of this molecule could be approached in two manners: 1) epoxidation of the parent tetrahydrofurfuryl-9-ocatcedecenoate, or 2) epoxidation of high-oleic soybean oil or other natural or genetically modified seed oil followed by transesterifi cation.
•■ O C6H -CH A 2 CH2-(CeH12hCH3
[0026] Epoxidized Tetrahydrofurfurylsoyate. Transesterification of epoxidized soybean oil (ESO) with tetrahydrofurfuryl alcohol can be catalyzed by sodium methoxide or a derived sodium tetxahydrorarfuryloxide. All (100%) of the carbon in this molecule is bio-derived. Ferro Corporation makes ESO, and has the capability to hydrogenate furfuryl aldehyde to furfuryl alcohol. Further hydrogenation or hydrogenation of furfuryl aldehyde with a different catalyst would yield tetrahydrofurfuryl alcohol. Glycerin is a byproduct that is removed by gravity separation. Steam distillation is useful in removing tetrahydrofurfuryl alcohol, aldehydes and other byproducts. Epoxidized tetrahydrofurfuryl soyate is shown below.
Figure imgf000009_0001
Generalized structure for Epoxidized Fatty Acid Esters.
Figure imgf000009_0002
[0027] In the generalized fatty acid ester formula above, R may be benzyl or furyl alcohols such as fixrfuryl, tetrahydro furfuryl, 1 -(2 -furyl) ethanol, l(tetrahydrofuran-2-yl) ethanol, below,
Figure imgf000009_0003
[0028] wherein,
[0029] when n =0, then m+p = 2x+l , where x is from 0 to 9;
[0030] when n = 1 and m =6, then p is 4 or 6;
[0031] when n = 1 and m = 8, then p = 6;
[0032] when n = 1 and m = 10, then p = 4;
[0033] when n = 2 then m = 6 and p = 3 ;
[0034] when n = 3 then m = 3 or 6 and m+p = 6; [0035] when n = 4 then m = 2 and p = 3;
[0036] when n = 5 then m = 2 and p = 0;
[0037] when n = 6 then m = 1 and p = 0.
[0038] Set forth below are representative plasticizers contemplated by the invention. The following lists are exemplary and without limitation.
[0039] Plasticizers based on bio-derived raw materials such as benzyl succinates, benzyl phthalates, benzyl cyclohexane-l,2-carboxylates, epoxidized furyl fatty acid esters and phosphate esters are contemplated herein.
[0040] Benzyl succinates such as benzyl butyl succinate, benzyl isobutyl succinate, benzyl pentyl succinate, benzyl 2-methylbutyl succinate, benzyl 3-methylbutyl succinate, benzyl hexyl succinate, benzyl heptyl succinate, benzyl 2-ethylhexyl succinate, benzyl n-octyl succinate, benzyl isononyl succinate, benzyl nonyl succinate, benzyl 2-propylheptyl succinate, benzyl decyl succinate.
[0041] Benzyl Phthalates such as benzyl butyl phthalate, benzyl isobutyl phthalate, benzyl pentyl phthalate, benzyl 2-methylbutyl phthalate, benzyl 3-methylbutyl phthalate, benzyl hexyl phthalate, benzyl heptyl phthalate, benzyl texanyl phthalate, benzyl 2-ethylhexyl phthalate, benzyl n-octyl phthalate, benzyl isononyl phthalate, benzyl nonyl phthalate, benzyl 2- propylheptyl phthalate, benzyl decyl phthalate.
[0042] Benzyl cyclohexane-l,2-dicarboxylate include but are not limited to benzyl butyl cyclohexane- 1,2-carboxylate, benzyl isobutyl cycIohexane-l,2-carboxylate, benzyl pentyl cyclohexane-l,2-carboxylate, benzyl 2-methylbutyl cyclohexane-l,2-carboxylate, benzyl 3- methylbutyl cyclohexane- 1,2-carboxylate, benzyl hexyl cyclohexane- 1,2-carboxylate, benzyl heptyl cyclohexane- i ,2-carboxylate, benzyl 2-ethylhexyl cyclohexane-l,2-carboxylate, benzyl n- octyl cyclohexane- 1 ,2-carboxylate, benzyl texanyl cyclohexane- 1,2-dicarboxylate, benzyl isononyl cyclohexane-l,2-carboxylate, benzyl nonyl cyclohexane- 1,2-carboxylate, benzyl 2- propylheptyl cyclohexane- 1 ,2-carboxylate, benzyl decyl cyclohexane- 1 ,2-carboxylate.
[0043] Benzoates include but are not limited to butyl benzoate, isobutyl benzoate, pentyl benzoate, 2-methylbutyl benzoate, 3-methylbutyl benzoate, hexyl benzoate, heptyl benzoate, texanyl benzoate, 2-ethylhexyl benzoate, n-octyl benzoate, 2,2,4-trimethylpentane-l,3-diyl dibenzoate, isononyl benzoate, nonyl benzoate, 2-propylheptyl benzoate, decyl benzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate. [0044] Epoxidized fatty acid esters of benzyl alcohol and furyl alcohols which include but are not limited to furfuryl alcohol, tetrahydrofurfuryl alcohol, l-(2-furyl)ethanol, l-(2- tetrahydrofuran-2-yl) ethanol. Epoxidized fatty acid esters include the bio-produced oils but are not limited to the following; soy oil, canola oil, castor oil, citrus seed oil, coconut oil, cod liver oil, corn oil, cottonseed oil, cuphea oil, linseed oil, oat oil, olive oil, palm oil, palm kernel oil, lard, peanut oil, rapeseed oil, rice bran oil, safflower oil, safflower high oleic oil, sesame oil, soybean oil, sunflower oil, sunflower high oleic oil, tung oil with furfuryl alcohol,
tetrahydrofurfuryl alcohol, benzyl alcohol, l-(2-furyl)ethanol, l-(2-tetrahydrofuran2-yl)ethanol.
[0045] Phosphate esters include but are not limited to dibutylphenyl phosphate, di-(2- ethylhexyl)phenyl phosphate, tri-(2-ethylhexyl) phosphate, triburyl phosphate, tri-isobutyl phosphate, tri-(2-butoxyethyl) phosphate, 2-ethylhexyl diphenyl phosphate, n-octyl diphenyl phosphate, isononyl diphenyl phosphate, nonyl diphenyl phosphate, 2-propylheptyl diphenyl phosphate, tri-(tertiary butylphenyl phosphate, tertiaiy-butylphenyl diphenyl phosphate, di- (tertiary-butylphenyl)phenyl phosphate, triphenyl phosphate.
[0046] A sketch illustrating the routes to the raw materials and to the plasticizers from bio-mass is shown in Figure 1.
[0047] Epoxidized fatty acid methyl esters (EFAME) are contemplated herein.
[0048] The benzyl moiety used in making succinates, phthalates, cyclohexane-1,2
dicarboxylates, and fatty acid esters is derived from biomass through the treatment of bio-mass to obtain syngas. The syngas is then used to prepare toluene directly or by converting syngas to methanol. The methanol is reacted with ZSM-5 catalyst to produce a benzene, toluene and all three isomers of xylene, BTX (benzene, toluene, xylene) mixture. The BTX mixture is distilled to give commercial toluene. The toluene is converted to benzyl chloride and the benzyl chloride can be used directly in esterification with dicarboxylic acid anhydrides or the benzyl chloride can be easily converted to benzyl alcohol and then the esterification of the carboxylic acids to the esters which are common to the listed plasticizer except for the phosphate esters.
[0049] Bio-derived aliphatic alcohols for use in succinates, phthalates, cyclohexane-1,2- dicarboxylates, benzoates, and phosphates are made by first forming syngas from biomass followed by formation of methanol. The methanol is converted to olefins using a Zeolite catalyst. The olefins can be oligomerized and metathesized into a range from 2 carbon 30 carbons by a process such as SHOP. The olefins can de distilled apart to give either a mixture or a single olefin. The olefin or mixtures of olefins with carbon number 2 to 15 are converted to aldehydes with 1 carbon more than the olefin by hydroformylation which utilizes syngas and a catalyst. The aldehyde can be either hydrogenated to alcohol or oxidized to the corresponding acid. Thus bio-mass derived aliphatic linear and branched aicohois with carbon number ranging from 3 to 16 are available to use in the general esterification, transesterification and esterification utilizing benzyl chloride to form alkyl benzyl diester reactions to form the plasticizers.
[0050] Succinic acid utilized in making succinic anhydride is being produced commercially from sugars and starches that are biomass derived.
[0051] The phenyl moiety used in making phosphate esters is derived from biomass through the treatment of bio-mass to obtain syngas. The syngas is then used to prepare aromatics. Benzene is formed in a BTX process from aromatics formed from the syngas. Cumene is formed from benzene and propylene. The propylene is formed from the biomass and syngas. Phenol is formed from cumene and acetone in the cumene peroxidation process.
[0052] Succinates. Among the succinates that might be synthesized include dibenzyl succinate, w hich is obtained from the reaction of benzyl chloride and the disodium salt of succinic acid. Such a process would not require production of benzyl alcohol, and would not require converting the bio-succinic acid to succinic anhydride, as shown below.
Figure imgf000012_0001
[0053] Asymmetric succinates might also be made via phase transfer catalysis but would require reaction of an aliphatic alcohol with succinic anhydride prior to the phase transfer catalysis reaction with benzyl chloride. Tetrahydromrfuryl alcohol and a variety of other alcohols would be useful in the reaction scheme below.
Figure imgf000012_0002
[0054] Benzyl sebacates can be made similarly. Sebacic acid is a derivative of castor oil, and is biobased.
Figure imgf000013_0001
[0055] An embodiment of the invention is a method of making a plasticizer comprising: (a) obtaining C4 to C16 dicarboxylic acid anhydride from a biomass source, (b) obtaining a C3 to Qo alkyl alcohol from a biomass source, (c) obtaining benzyl chloride from a biomass source, (d) reacting the dicarboxylic acid anhydride with the alkyl alcohol, to form an alkoxycarbonyl carboxylic acid, (e) reacting the alkoxycarbonyl carboxylic acid with N, N-diethylethanamine to form N-N-diethylethaminium the alkoxycarbonyl carboxylate, and (f) reacting the N-N- diemyletharninium alkoxycarbonyl alkylcarboxylate, with benzyl chloride to form benzyl alkyl dicarboxylate. The dicarboxylic acid anhydride is suitably a dialkyl acid anhydride. The dicarboxylic acid anhydride may be an aryl di-acid anhydride, such as succinic anhydride, phthalic anhydride, or adipic anhydride.
[0056] An embodiment of the invention is a method of making a plasticizer comprising: (a) obtaining sebacic acid anhydride from a biomass source, (b) obtaining a C3 to C10 alkyl alcohol from a biomass source, (c) obtaining benzyl chloride from a biomass source, (d) reacting the sebacic acid anhydride with the alkyl alcohol, to form an alkoxysebacic acid, (e) reacting the alkoxysebacic acid with N, N-diethylethanamine to form N-N-diethylethaminium alkoxysebacic carboxylate, and (f) reacting the N-N-diethylethaminium alkoxysebacic carboxylate, with benzyl chloride to form benzyl alkyl sebacate.
[0057] Another embodiment of the invention involves provision of benzyl alcohol for other process steps, the benzyl alcohol, provided by a process comprising, (a) treating biomass to obtain lignocellulose, (b) treating lignocellulose to obtain syngas, (c) treating syngas to obtain toluene, with an optional intermediate step of obtaining methanol, (d) treating methanol with a zeolite catalyst to produce a BTX mixture, (e) distilling the BTX mixture to give toluene, (f) converting the toluene to benzyl chloride, and (g) converting the benzyl chloride to benzyl alcohol.
[0058] An embodiment of the invention is a plastic mass or plastic article including any plasticizer made by any method disclosed herein. [0059] Phase Transfer Catalysis (PTC) synthesis of benzyl acetate and benzyl benzoate is suitable in the invention. Broadly, all dibasic acids with 4 to 10 carbon atoms is envisioned, especially succinic acid, a C4 dibasic acid. The catalysts used are potassium iodide or sodium bromide (for halogen exchange) and quaternary ammonium salts (for phase transfer). In some instances, the quaternary ammonium salts can be produced in situ from benzyl chloride and tributylamine. Aqueous solution of the sodium salt of the acid and KI or NaBr can be combined with a toluene solution of the tertiary amine. Upon heating the reaction a desired set temperature, benzyl chloride is added. Yields as high as 96% benzyl n-butyl phthalate (using KI), 99% benzyl benzoate (using NaBr), and 96% benzyl acetate (using KI) can be obtained.
[0060] In any embodiment where N, N-diethylethanamine (triethylamine) is used, any organic or inorganic base may be used, such as Bronsted-Lowry bases, including triaUcylamines. Suitable Bronsted-Lowry bases include ammonium ion and primary, secondary and tertiary ammonium ions and their salts. Quaternary ammonium hydroxides such as tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, tripropyl amine, tributyl amine, benzyl dimethyl amine, dibenzyl methyl amine, and benzyl diethyl amine.
[0061] Generally, trialkyl amines as well as amines having a benzyl group and two alkyl groups or two benzyl groups and an alkyl group are useful. In a preferred embodiment, the alkyl groups in the aforementioned examples independently have 1-20 carbon atoms, preferably 1-10 carbon atoms, more preferably 1-8 carbon atoms.
[0062] Additives. The most important additives contemplated herein include antioxidants, such as primary and secondary antioxidants, which may be included separately or together. In one embodiment, any plasticizer disclosed herein directly or made by any method herein may be accompanied by at least one primary antioxidant and/or at least one secondary antioxidant.
[0063] Antioxidants can be divided in two basic classifications: primary and secondary antioxidants. Primary antioxidants interrupt oxidation degradation by tying up the free radicals. They react rapidly with peroxy radicals to break growing chains. Secondary antioxidants destroy the unstable hydroperoxides that function as sources of free radicals during oxidative degradation. They react with hydroperoxides to yield nonreactive products. Thus, secondary antioxidants are also known as hydroperoxide decomposers. [0064] The two major groupings among the primary antioxidants are hindered phenolics and aromatic amines. Primary antioxidants function by donating their reactive hydrogen to the peroxy free radicals so that the propagation of subsequent free radicals does not occur.
[0065] The most widely used antioxidants for polymer protection are phenolics. These products generally resist staining or discoloration. However, they may form quinoid structures upon oxidation, which leads to yellowing.
[0066] Amines, normally arylamines, may be more effective than phenolic, but most are staining and discoloring and lack FDA approval for use in contact with food. Amines are commonly used in the rubber industry, but they are also used in applications such as wire and cable formulations and in polyurethance polyols.
[0067] Secondary antioxidants. Secondary antioxidants are used in conjunction with primary antioxidants to provide added stability to the polymer and ether containing compounds. They function by decomposing hydroperoxides to form nonreactive products. Typical secondary antioxidant compounds contain sulfur or phosphorous. The more popular secondary antioxidants are thioesters (thiodipropinonic acid derivatives and polythiodipropionates) and
organophosphites.
[0068] Secondary Phosphite Antioxidants useful in the present invention include tris (2,4-di-tert- butylphenyl) phosphite, distearyl pentaerythritol diphosphate, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite; poly(dipropylene glycol) phenyl phosphite, 2-ethylhexyl diphenyl phosphite, triisodecyl phosphite, phenyl diisodecyl phosphite, diphenyl isodecyl phosphite, triphenyl phosphite, and tris(nonylphenyl)phosphite. Most preferred is trilauryl phosphite.
[0069] Antioxidant Blends. Every stabilizer has a specific temperature range in which it develops its optimum properties. For this reason, antioxidant system (stabilizer packages) combining two or more materials are often used. Such blends are commercially available as a single additive. The most effective mixture will combine a free radical inhibitor (primary antioxidant) with a peroxide decomposer (secondary antioxidant). The free radical inhibitor retards the initiation of reaction chains, but some hydroperoxide is nevertheless formed. A peroxide decomposer available to react with the hydroperoxide prevents it from decomposing with free radicals. This feature can provide a measure of safety when a hydroperoxide, which is known to decompose violently, is safely decomposed using a peroxide decomposer.

Claims

Claims
1. A method of making an epoxidized fatty acid ester comprising:
a. providing at least one alcohol selected from the group consisting of furfuryl alcohol, tetrahydrofurfuryl alcohol, ethanol, butanol, benzyl alcohol, 2-ethylhexanol, 2- propylheptanol, C3- C31 alcohols,
b. providing at least one fatty acid,
c. wherein at least one of the alcohol and the fatty acid is biomass sourced, d. reacting the at least one alcohol with the at least one fatty acid in the presence of an alkoxide catalyst, to afford an esterified fatty acid,
e. combining the esterified ester with a natural unsaturated triglyceride, and f. reacting the mixture of esterified fatty acid and natural unsaturated triglyceride with an oxidizer and an acid to form an epoxidized fatty acid ester and epoxidized fatty acid triglyceride mixture.
2. The method of claim 1, wherein the at least one alcohol is furfuryl alcohol or
tetrahydiOfurfuryl alcohol, and wherein the at least one fatty acid is selected from the group consisting of myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, linolenic acid, arachidonic acid, eicopentaenoic acic, erucic acid, docosohexanoic acid, a group of fatty acids sourced from soybeans, a group of fatty acids sourced from linseeds, and combinations thereof.
3. The method of claims 1 or 2, wherein the alkoxide catalyst is selected from the group
consisting of sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, and combinations thereof.
4. The method of any of claims 1-3, wherein the alcohol is tetrahydrofurfuryl alcohol and the at least one fatty acid is linoleic acid.
The method of any of claims 1-4, wherein the alcohol is tetrahydrofurfuryi alcohol and the at least one fatty acid is 5-10 wt% alpha-linolenic acid, 45-55 wt% linolenic acid, 20-25 wt% oleic acid, 2-7 wt% stearic acid and 5-15 wt% palmitic acid.
The method of any of claims 1 -5, wherein the epoxidized fatty acid ester has the generalized formula,
Figure imgf000017_0001
wherein R is benzyl alcohol or furyl alcohols selected from the group consisting of furfuryl, tetrahydrofurfuryi, l-(2-furyl) ethanol, 1 (tetrahydrofuran-2-yl) ethanol, wherein,
when n =0, then m+p = 2x+l, where x is from 0 to 9;
when n = 1 and m =6, then p is 4 or 6;
when n = 1 and m = 8, then p = 6;
when n = 1 and m = 10, then p = 4;
when n = 2 then m = 6 and p = 3;
when n = 3 then m = 3 or 6 and m+p = 6;
when n = 4 then m = 2 and p = 3;
when n = 5 then m = 2 and p = 0;
when n = 6 then m = 1 and p = 0.
7. A plastic composition including the plasticizer made by the method of any of claims 1-6.
8. A method of making a plasticizer comprising:
a. obtaining cyclohexane-l,2-dicarboxylic acid anhydride from a biomass source, b. obtaining butanol from a biomass source,
c. obtaining benzyl chloride from a biomass source
d. reacting the cyclohexane-l,2-dicarboxylic acid anhydride with the butanol, optionally in the presence of heat, to form 2-(butoxycarbonyl) cyclohexanecarboxylic acid, e. reacting the 2-(butoxycarbonyl) cyclohexanecarboxylic acid with a Bronsted-Lowry base to form a conjugate pair,
f. reacting the conjugate pair, with benzyl chloride to form benzyl butyl cyclohexane-1, 2-dicarboxylate.
9. A plastic composition including the plasticizer made by the method of claim 8.
10. A method of making a plasticizer comprising:
a. obtaining C4 to C16 dicarboxylic acid anhydride from a biomass source,
b. obtaining a C3 to C10 alkyl alcohol from a biomass source,
c. obtaining benzyl chloride from a biomass source,
d. reacting the dicarboxylic acid anhydride with the alkyl alcohol, to form an
alkoxycarbonyl carboxylic acid,
e. reacting the alkoxycarbonyl carboxylic acid with N, N-diethylethanamine to form N- N-diethylethaminium the alkoxycarbonyl carboxylate,
f. reacting the N-N-diethylethamimum the alkoxycarbonyl alkylcarboxylate, with
benzyl chloride to form benzyl alkyl dicarboxylate.
11. The method of claim 10, wherein the dicarboxylic acid anhydride is a dialkyl acid anhydride
12. The method of claims 10, wherein the dicarboxylic acid anhydride is an aryl di-acid
anhydride.
13. The method of claim 11, wherein the dicarboxylic acid anhydride is succinic anhydride.
14. The method of claim 12, wherein the dicarboxylic acid anhydride is phthalic anhydride.
15. The method of claim 11, wherein the dicarboxyUc acid anhydride is adipic anhydride.
16. A plastic composition including the plasticizer made by the method of any of claims 10-15.
17. The process of claim 1, wherein the at least one alcohol is benzyl alcohol, wherein the at least one benzyl alcohol is provided by a process comprising,
a. treating biomass to obtain lignocellulose,
b. treating lignocellulose to obtain syngas,
c. treating syngas to obtain toluene, with an optional intermediate step of obtaining methanol,
d. treating methanol with a zeolite catalyst to produce a BTX mixture,
e. distilling the BTX mixture to give toluene,
f. converting the toluene to benzyl chloride, and
g. converting the benzyl chloride to benzyl alcohol.
18. A method of making a plasticizer comprising:
a. obtaining C4 to C10 dicarboxylic acid anhydride from a biomass source, b. obtaining a C3 to do alkyl alcohol from a biomass source,
c. obtaining benzyl chloride from a biomass source,
d. reacting the dicarboxylic acid anhydride with the alkyl alcohol, to form an
alkoxycarbonyl carboxylic acid,
e. reacting the alkoxycarbonyl carboxylic acid with N, N-diethylethanamine to form N- N-diethylethaminium alkoxycarbonyl carboxylate,
f. reacting the N-N-diethylethaminium alkoxycarbonyl alkylcarboxylate, with benzyl chloride to form benzyl alkyl dicarboxylate.
19. A process of preparing a biomass sourced benzyl succinate comprising
a. reacting biomass sourced disodium succinate withbiomass sourced benzyl chloride b. in the presence of a phase transfer catalyst
c. to afford dibenzyl succinate.
20. A process of preparing a biomass sourced benzyl succinate comprising
a. reacting biomass sourced disodium sebacate with biomass sourced benzyl chloride b. in the presence of a phase transfer catalyst
c. to afford dibenzyl sebacate.
21. A process of preparing epoxidized tetrahydrofurfurylsoyate comprising:
a. reacting biomass sourced epoxidized soybean oil with
b. tetrahydrofurfur l alcohol in the presence of
c. at least one of sodium methoxide and sodium tetrahydrofurfuryloxide,
d. to produce epoxidized tetrahydrofarf rylsoy te.
22. The process of claim 21, wherein the teirahydrofurfuryl alcohol is produced by a process comprising:
a. hydrogenating furfuryl aldehyde to produce furfuryl alcohol, and
b. hydrogenating the furfuryl alcohol to produce tetrahydrofurfuryl alcohol.
23. The plastic composition of claim 7, further comprising a secondary antioxidant.
24. The plastic composition of claim 9, further comprising a secondary antioxidant.
25. The plastic composition of claim 16, further comprising a secondary antioxidant.
26. The plastic article of claim 23, wherein the secondary antioxidant is an organophosphorus compound or thiosynergist.
27. The plasticizer of claim 1, further comprising a secondary antioxidant.
28. The epoxidized tetrahydrofurfurylsoyate plasticizer made by the process of claim 21, further comprising a secondary antioxidant.
29. A plastic composition including the plasticizer of claim 28.
PCT/US2014/043122 2013-07-01 2014-06-19 Biobased epoxidized fatty acid ester plasticizers WO2015002746A2 (en)

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