JP2014055138A - Composition containing monoester and diester of 1,3-propanediol in biological basis - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide ester compositions of biologically derived 1,3-propanediol, and to provide a manufacturing method and its use.SOLUTION: A process of producing 1,3-propanediol biologically, a process of producing esters by contacting 1,3-propanediol and an organic acid, and a process of collecting the produced esters are included. Esters of 1,3-propanediol are useful in personal care products, cosmetics, food products, surfactants and soap articles, as a plasticizer in a polymer product, a solvent or a diluent in an extraction process and for extraction solutions.

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application is filed in US Provisional Application No. 60 / 772,471 filed February 10, 2006; US Provisional Application No. 60 / 772,194 filed February 10, 2006; US Provisional Application No. 60 / 772,193 filed February 10, 2006; US Provisional Application No. 60 / 772,111 filed February 10, 2006; filed February 10, 2006 U.S. Provisional Application No. 60 / 772,120; U.S. Provisional Application No. 60 / 772,110 filed on Feb. 10, 2006; U.S. Provisional Application No. 60/772 filed on Feb. 10, 2006. , 112; US provisional application 60 / 846,948 filed September 25, 2006; US provisional application 60 / 853,920 filed October 24, 2006; November 2006 On the 15th US Provisional Application No. 60 / 859,264 filed; US Provisional Application No. 60 / 872,705 filed on December 4, 2006; and US Provisional Application No. 60 / 872,705 filed on January 17, 2007. Claims 60 / 880,824, the disclosures of which are expressly incorporated herein by reference in their entirety.

  The present invention relates generally to the field of esters of 1,3-propanediol. More specifically, the present invention relates to biologically derived esters of 1,3-propanediol.

  There is an increasing interest in the environmental impact of all products in consumers and manufacturers. Efforts toward awareness of environmental impacts are a universal concern recognized by government agencies. The draft amendment to the UN Framework Convention on Climate Change (UNFCCC), currently signed by 156 countries, is a global effort to prioritize safer, more environmentally friendly manufacturing that goes beyond cost and efficiency. It is an example. Consumers are becoming increasingly selective regarding the origin of the products they purchase, especially when applied to products such as personal care, cosmetics, therapeutics, and medicated cosmetics. The 2004 Co-operative Bank annual Ethical Consumer Report (www.co-operativebank.co.uk) is 3.7% of all consumers spending between 2003 and 2004. 30% for consumers spending ethical retail products (general classification of environmentally safe, organic, and fair trade products) over the same period, compared to only 30%. Disclosed a 3% increase.

  One of the single biggest environmental concerns for consumers is the impact of global warming and the greenhouse gases that contribute to this impact. Greenhouse gas is a gas that allows sunlight to enter the atmosphere freely. When sunlight hits the earth's surface, some of it reflects back into space as infrared radiation. Greenhouse gas absorbs this infrared radiation and traps heat in the atmosphere. Over time, the amount of energy sent from the sun to the surface should be about the same as the amount of energy emitted back into space, leaving the surface temperature approximately constant. However, the increase in the amount of greenhouse gas beyond that which existed before human industrialization occurred increased the heat retained on the surface, and the global warming observed during the last two centuries It is thought that has brought

  Carbon dioxide has been pointed out as the largest component of atmospheric greenhouse gas collections. Atmospheric carbon dioxide levels have increased by 50% in the last 200 years. Additional carbon dioxide in the atmosphere is believed to further shift the effects of greenhouse gases from global temperature stabilization to the effects of temperature rise. Consumers and environmental groups have also identified the industrial release of carbon into the atmosphere as a source of carbon that causes the greenhouse effect. Only organic molecules that consist of renewable sources such as plant sugar and starch, and ultimately atmospheric carbon, when compared to similar organic molecules that are based on petroleum or fossil fuels. It is considered not to contribute further to the greenhouse effect.

  In addition to adding carbon dioxide to the atmosphere, current methods of industrial production of propanediol include contaminants and waste, including, among others, sulfuric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid, tartaric acid, acetic acid , Alkali metals, alkaline earth metals, transition metals, and heavy metals, including iron, cobalt, nickel, copper, silver, molybdenum, tungsten, vanadium, chromium, rhodium, palladium, osmium, iridium, rubidium, And platinum (US Pat. Nos. 2,434,110, 5,034,134, 5,334,778, and 5,10,036).

  All manufacturing needs to provide products with reduced environmental impacts, and in particular to consider the carbon burden on the atmosphere. There are also environmental advantages for manufacturers providing products of renewable sources. Further, there is a need for a well-established solvent that is produced with little or no increase in existing carbon dioxide levels in the environment.

  Published US Patent Application No. 2005/0069997 discloses a method for purifying 1,3-propanediol from cultured E. coli fermentation broth that is bioengineered to synthesize 1,3-propanediol from sugar. doing. The basic method involves filtration, ion exchange, and distillation of the fermentation broth product stream, and preferably involves chemical reduction of the product during the distillation procedure. Also provided is a highly purified composition of 1,3-propanediol.

FIG. 1 is a diagram of the nuclear magnetic resonance spectrum of the product obtained in Example 3. The figure plots the following values: (CDCl ₃ ): δ = 0.88 (t, CH ₃ —CH ₂ , 6H), 1.26 (t, CH ₂ —CH ₂ —CH ₂ , 28H), _{1.61 (t, CH 2 -CH 2} -C = O, 4H), 1.97 (t, -O-CH 2 -CH 2 -CH 2 -O, 2H), 2.28 (t, CH 2 -C = O, 4H), 4.15 (t, C (= O) -O-CH 2 -4H). FIG. 2 is a DSC (Differential Scanning Calorimetry) curve of the product obtained in Example 3. DSC (Tm = 66.4 ° C. and Tc = 54.7 ° C.). FIG. 3 is a diagram of the nuclear magnetic resonance spectrum of the product obtained in Example 4. The figure plots the following values: δ = 0.88 (t, CH ₃ —CH ₂ , 6H), 1.26 (t, CH ₂ —CH ₂ —CH ₂ , 28H), 1.61 (t , CH ₂ —CH ₂ —C═O, 4H), 1.97 (t, —O—CH ₂ —CH ₂ —CH ₂ —O, 2H), 2.28 (t, CH ₂ —C═O, 4H), 4.15 (t, C (= O) -O-CH 2 -4H). FIG. 4 is a diagram of the nuclear magnetic resonance spectrum of the recrystallized product obtained in Example 5. The figure plots the following values: δ = 0.88 (t, CH ₃ —CH ₂ ), 1.27 (t, CH ₂ —CH ₂ —CH ₂ ), 1.60 (t, CH ₂ — CH ₂ -C = O), 1.87 and _{1.96 (t, -O-CH 2} -CH 2 -CH 2 -O), 2.31 (t, CH 2 -C = O), 3.70 _{(t, HO-CH 2 -CH} 2 -), 4.15 and 4.24 (t, C (= O ) -O-CH 2 -). FIG. 5 is a diagram of the nuclear magnetic resonance spectrum of the product obtained in Example 6. The figure plots the following values: δ = 0.88 (t, CH ₃ —CH ₂ ), 1.27 (t, CH ₂ —CH ₂ —CH ₂ ), 1.63 (t, CH ₂ — CH ₂ -C = O), 1.82,1.87 and _{1.96 (t, -O-CH 2} -CH 2 -CH 2 -O), 2.31 (t, CH 2 -C = O) , 3.69 and 3.86 (t, HO—CH ₂ —CH ₂ —), 4.15 and 4.21 (t, C (═O) —O—CH ₂ —). FIG. 6 is a diagram of the nuclear magnetic resonance spectrum of the product obtained in Example 7. The figure plots the following values: δ = 0.88 (t, CH ₃ —CH ₂ ), 1.27 (t, CH ₂ —CH ₂ —CH ₂ ), 1.60 (t, CH ₂ — CH ₂ -C = O), 1.87 and _{1.96 (t, -O-CH 2} -CH 2 -CH 2 -O), 2.31 (t, CH 2 -C = O), 3.70 _{(t, HO-CH 2 -CH} 2 -), 4.15 and 4.24 (t, C (= O ) -O-CH 2 -). FIG. 7 is a diagram of the nuclear magnetic resonance spectrum of the product obtained in Example 8. The figure plots the following values: δ = 0.88 (t, CH ₃ —CH ₂ ), 1.27 (t, CH ₂ —CH ₂ —CH ₂ ), 1.63 (t, CH ₂ — CH ₂ -C = O), 1.82,1.87 and _{1.96 (t, -O-CH 2} -CH 2 -CH 2 -O), 2.31 (t, CH 2 -C = O) , 3.70 and 3.86 (t, HO—CH ₂ —CH ₂ —), 4.15 and 4.24 (t, C (═O) —O—CH ₂ —).

  Compositions comprising esters of 1,3-propanediol are provided. The 1,3-propanediol used to form the ester is biologically derived. The ester may have at least 3% biobased carbon. The composition may further comprise a biologically derived 1,3-propanediol. A method for producing a composition comprising an ester of 1,3-propanediol is also provided. These methods include providing biologically produced 1,3-propanediol, contacting 1,3-propanediol with an organic acid, and recovering the produced ester.

Deposit of organisms Transformed E. coli DH5α containing cosmid pKP1 containing part of the Klebsiella genome encoding the glycerol dehydratase enzyme was deposited with the ATCC on April 18, 1995 under the terms of the Budapest Treaty and identified by ATCC number ATCC 69789 Has been. A transformed E. coli DH5α containing cosmid pKP4 containing part of the Klebsiella genome encoding the diol dehydratase enzyme has been deposited with the ATCC on 18 April 1995 under the terms of the Budapest Treaty and has been identified by ATCC number ATCC 69790 . As used herein, “ATCC” refers to 10801 University Boulevard, Manassas, VA, 20110 2209, U.S. Pat. S. A. American Type Culture Collection international depository located in the US. The “ATCC number” is the accession number for the culture at the time of depositing with the ATCC.

Detailed Description of the Invention Applicants specifically incorporate the entire contents of all cited references in this disclosure. Furthermore, when an amount, concentration, or other value or parameter is given as a range, preferred range, or a list of preferred values above and below preferred values, this is the range disclosed separately. It is understood as specifically disclosing all ranges formed from any upper limit or preferred value and any pair of any lower limit or preferred value, whether or not. When a range of numerical values is listed herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range.

  Fatty acid monoesters and diesters of 1,3-propanediol produced in a manner that does not substantially increase the net amount of carbon dioxide are pharmaceuticals, soaps, surfactants, shampoos, and personal care or cosmetic products, and some Useful in the preparation of certain industrial applications. In such products, fatty acid monoesters and diesters of 1,3-propanediol are emulsifiers, surfactants, regulators, structurants, thickeners, humectants, temperature stabilizers, chemical stabilizers, opacifiers, Specific as a brightening agent, solvent, dispersant, wetting agent, gelling agent, compatibilizer, corrosion inhibitor, lubricant, demulsifier, biocide, antimicrobial agent, or antifoam agent Can be used for

  Biologically produced fatty acid monoesters and diesters of 1,3-propanediol are formed by biologically induced esterification of 1,3-propanediol. Biologically derived 1,3-propanediol can be obtained through catalytic conversion of non-fossil fuel carbon via fermentation using organisms capable of synthesizing 1,3-propanediol. . The method provides 1,3-propanediol and its conjugated monoesters and diesters without introducing additional carbon into the atmosphere during manufacture, use, or disposal of the material.

  Biologically produced 1,3-propanediol represents a new source for a useful monoester of 1,3-propanediol. Such monoesters and diesters have not been previously produced from biosourced monomers. In this way, new compositions comprising 1,3-propanediol esters derived from biologically sourced carbon substrates are provided. These compositions can be distinguished from similar compositions derived from all petrochemical carbons based on the carbon content of the biological source.

  The terms used in this application are given the following definitions.

  “Bio-PDO ester”, “Bio-based PDO ester”, “Biologically derived PDO ester”, and “Biological-based 1,3-propanediol ester”, and similar terms, are As used herein, monoesters and diesters produced from biologically produced 1,3-propanediol.

  “Biological PDO”, “Biogenic PDO”, “Biologically produced 1,3-propanediol”, “Biologically derived 1,3-propanediol”, and “Biologically derived 1” The term “, 3-propanediol”, and similar terms, as used herein, is derived from the microbial metabolism of plant-derived sugars that are composed of atmospheric carbon and not fossil fuels. , 3-propanediol.

  “Substantially purified” as used by the Applicants to describe biologically produced 1,3-propanediol produced by the method of the invention has the following characteristics: A composition comprising 1,3-propanediol having at least one of: 1) UV absorption of less than about 0.200 at 220 nm, and less than about 0.075 at 250 nm, and less than about 0.075 at 275 nm; Or 2) a composition having an L * a * b * “b *” color value of less than about 0.15 and an absorption of less than about 0.075 at 270 nm; or 3) a peroxide composition of less than about 10 ppm; or 4) about Concentration of total organic impurities below 400 ppm.

  The “b *” value is a spectrophotometrically determined “yellow-blue measurement, as defined by CIE L * a * b * measurement ASTM D6290.

  The abbreviation “AMS” refers to accelerator mass spectrometry.

  “Biologically produced” means an organic compound produced by one or more species or strains of an organism, including certain strains of bacteria, yeast, fungi, and other microorganisms. “Bio-produced” and biologically produced are used synonymously herein. Such organic compounds are composed of carbon derived from atmospheric carbon dioxide converted to saccharides and starch by green plants.

  “Biological base” means that organic compounds are synthesized from biologically produced organic components. Synthesis methods disclosed herein include bio-produced alcohols other than 1,3-propanediol; in particular, ethylene glycol, diethylene glycol, triethylene glycol,-, dipropylene diol, tripropylene diol, 2-methyl 1, It is further contemplated that other monoesters and diesters from alcohols including 3-propanediol, neopentyl glycol, and bisphenol A can be efficiently synthesized. “Bio-based” and “biological-source”; “biologically derived”; and “biological-derived” are used synonymously herein.

  “Fermentation”, when used, refers to a method of metabolizing monosaccharides to other organic compounds. As used herein, fermentation specifically refers to the metabolism of plant-derived sugars, such sugars being composed of atmospheric carbon.

  “Atmospheric carbon” as used herein refers to a carbon atom from a carbon dioxide molecule that has recently been liberated in the Earth's atmosphere during the past decades. Such carbon masses can be identified by the presence of certain radioisotopes described herein. “Green carbon”, “Atmospheric carbon”, “Environmentally friendly carbon”, “Life cycle carbon”, “Non-fossil fuel-based carbon”, “Non-petroleum-based carbon”, “Atmospheric carbon”, and “Bio-based” “Carbon” is used synonymously herein.

  “Fossil-derived carbon” as used herein refers to petrochemical-derived carbon. Because such carbon is not as exposed to ultraviolet radiation as atmospheric carbon, most of the fossil carbon has few radioisotopes in their population. The fossil carbon can be identified by the means described herein. “Fossil fuel carbon”, “fossil carbon”, “polluting carbon”, “petrochemical carbon”, “petroleum-carbon”, and fossil-derived carbon are used synonymously herein.

  “Naturally occurring” as used herein refers to a material derived from a renewable source and / or produced by a biologically based method.

  “Fatty acid” as used herein refers to a carboxylic acid that often has a long chain fatty acid tail, although carboxylic acids having 4 to 40 carbon atoms are specifically defined in this definition for purposes of illustrating the present invention. include. A “fatty acid ester” as used herein is an ester composed of the fatty acids thus defined.

  “Catalyst” as used herein refers to a substance that promotes a chemical reaction without being a reactant or product of the reaction.

  The acronym “NMR” means nuclear magnetic resonance.

  The terms “color” and “color body” are visible using a spectrophotometer in the visible light range, using wavelengths of about 400-800 nm, and by comparison with pure water. Means the presence of color. Reaction conditions can have an important effect on the nature of color production. Examples of relevant conditions include the temperature used, the catalyst, and the amount of catalyst. Without wishing to be bound by theory, the inventors believe that color precursors contain trace amounts of impurities including olefinic bonds, acetals, and other carbonyl compounds, peroxides, and the like. At least some of these impurities can be detected by methods such as UV spectroscopy or peroxide titration.

  “Color index” refers to an analytical measure of the electromagnetic radiation-absorption characteristics of a substance or compound.

  “Hydrogenation reactor” refers to any known chemical reactor known in the literature, including shaker tubes, batch autoclaves, slurry reactors, upflow packed beds, and trickle flow packing. Including but not limited to a bed reactor.

The abbreviation “IRMS” refers to the measurement of CO ₂ by high precision stable isotope ratio mass spectrometry.

  The term “carbon substrate” means any carbon source that can be metabolized by a microorganism, wherein the substrate comprises at least one carbon atom.

  Unless otherwise stated, all percentages, parts, ratios, etc. are by weight. Trademarks are shown in capital letters. Further, if an amount, concentration, or other value or parameter is given as either a certain range, a preferred range, or a list of preferred values for the upper and lower limits, this is the range disclosed separately. It is understood to specifically disclose that all ranges are formed from any upper or preferred range and any lower or preferred range, regardless of whether or not.

A small amount of carbon dioxide in the atmosphere is radioactive. This 14C carbon dioxide is created when nitrogen is attacked by ultraviolet light that produces neutrons, causing the nitrogen to lose protons and form carbon of molecular weight 14, and is immediately oxidized to carbon dioxide. This radioactive isotope represents a small but measurable fraction of atmospheric carbon. Atmospheric carbon dioxide circulates through green plants, creating organic molecules during a process known as photosynthesis. The cycle is completed when a green plant or other form of life metabolizes organic molecules, producing carbon dioxide, which is released back into the atmosphere. Virtually all forms of life on Earth depend on the production of organic molecules by this green plant to produce chemical energy that promotes growth and regeneration. Therefore, 14C present in the atmosphere becomes a part of all forms of life and their biological products. These renewable organic molecules that biodegrade to CO ₂ do not contribute to global warming. This is because there is no net increase in carbon dioxide released to the atmosphere. In contrast, fossil fuel-based carbon does not have the characteristic radiocarbon ratio of atmospheric carbon dioxide.

  Assessment of renewable carbon in materials can be performed through standard test methods. Radiocarbon and isotope ratio mass spectrometry can be used to determine the biobased content of a substance. ASTM International, formerly known as the American Society for Testing and Materials, has established a standard method for evaluating the bio-based contents of materials. The ASTM method is referred to as ASTM-D6866.

  The application of ASTM-D6866 to derive “biological content” is built on the same concept as radiocarbon dating, but does not involve the use of an age equation. The analysis is performed by deriving the ratio of the amount of radioactive carbon (14C) in the unknown sample to the amount of the latest reference standard. Ratios are reported as percentages using the unit “pMC” (modern carbon level). If the material being analyzed is a mixture of today's radiocarbon and fossil carbon (without radiocarbon), the resulting pMC value directly correlates with the amount of biomass material present in the sample.

  The modern reference standard used for the radiocarbon age is the NIST (National Institute of Standards and Technology) standard with known radiocarbon content, which is approximately equivalent to AD 1950. AD1950 was chosen because it represents a point in time prior to a thermonuclear weapon experiment (referred to as “explosive carbon”) that introduced an excess of radioactive carbon into the atmosphere with each explosion. The AD1950 reference represents 100 pMC.

  “Explosive carbon” in the atmosphere reached almost double the normal level in 1963 at the peak of the experiment and before the treaty to stop the experiment. Its distribution in the atmosphere has been approximated since its appearance shows values greater than 100 pMC for plants and animals since AD 1950. This gradually decreases over time, and today's value is close to 107.5 pMC. This can give a fresh biomass material such as corn a radiocarbon signature of close to 107.5 pMC.

  Combining fossil carbon with current carbon to material results in dilution of the current pMC content. By assuming that 107.5 pMC represents the current biomass material and 0 pMC represents the petroleum derivative, the measured pMC value for this material reflects the proportion of the two component types. Material that is 100% derived from current soybeans gives a radioactive carbon signature close to 107.5 pMC. If this material is diluted with 50% petroleum derivative, it gives a radioactive carbon signature close to 54 pMC.

  The biomass content result is derived by assigning 100% equal to 107.5 pMC and 0% equal to 0 pMC. In this respect, the sample measuring 99pMC gives a result of 93% equivalent biobase content.

  Evaluation of the materials described herein is done according to ASTM-D6866. The average value quoted in this report includes an absolute range of 6% (plus or minus 3% on either side of the bio-based content value) to account for variations in the terminal component, the radiocarbon signature. . That all materials are current or inherently fossil, and that the desired result is the amount of biobased ingredients “present” in the material, not the amount of biobased material “used” in the manufacturing process. Assume.

  The composition according to the invention comprises a composition comprising an ester of 1,3-propanediol. Esters can have varying amounts of biobased carbon, depending on the compound used in the esterification. Biologically derived 1,3-propanediol contains bio-based carbon. All three carbon atoms in 1,3-propanediol are bio-based carbons. If the conjugated ester is formed using a carboxylic acid that contains all biobased carbons, the resulting ester will also contain all biobased carbons. However, if the carboxylic acid contains non-bio-based carbon, i.e. carbon from a fossil fuel source, the resulting ester is compared to three carbons derived from biologically derived 1,3-propanediol. And a percentage of bio-based carbon that is proportional to the number of carbons provided by the carboxylic acid.

  For example, propanediol distearate contains 39 carbon atoms, with 18 from each of the stearic acid carbon chains and three from 1,3-propanediol. Thus, if stearic acid is not biobased, a total of 36 to 36 carbons of propanediol distearate are non-biobased carbons. The predicted biobased content of propanediol distearate made from biologically derived propanediol and non-biologically derived stearic acid is 7.7 percent.

  In an analysis performed using ASTM-D6866, propylene glycol dibenzoic acid (BENZOFLEX® 284, Velsicol Chem. Corp. Rosemont, IL.) Was found to have a biobased carbon content of 0%. It was issued. A similar analysis of propanediol dibenzoic acid synthesized using biologically derived 1,3-propanediol had a biobased carbon content of 19%. The predicted biobased carbon content of propanediol dibenzoic acid made from biologically derived 1,3-propanediol is 17.6%, which is within the standard deviation of this method. is there.

  When the stearic acid in the above example is biobased, the resulting propanediol distearate has a biobased content of 100%. Thus, biologically derived conjugate esters of 1,3-propanediol have a biobased content value proportional to the biobased content of the acid used to form the ester. Thus, the ester comprises at least 3% biobased carbon, at least 6% biobased carbon, at least 10% biobased carbon, at least 25% biobased carbon, at least 50% biobased carbon, at least 75%. It may have a biobased carbon and a biobased content of at least 100% biobased carbon.

  If the organic acid is stearic acid or oleic acid, the recovered ester should be greater than 5% biobased carbon. If the organic acid is lauric acid, the recovered ester should be greater than 10% biobased carbon.

Biologically derived 1,3-propanediol Biologically derived 1,3-propanediol is collected in highly purified form. Such 1,3-propanediol has at least one of the following characteristics: 1) less than about 0.200 at 220 nm, less than about 0.075 at 250 nm, and less than about 0.075 at 275 nm. Absorption; or 2) a composition having an L * a * b * “b *” color value of less than about 0.15 and an absorption of less than about 0.075 at 270 nm; 3) a peroxide composition of less than about 10 ppm; or 4) Concentration of total organic impurities less than about 400 ppm. The “b *” value is a spectrophotometrically determined yellow-blue measurement as defined by CIE L * a * b * measurement ASTM-D6290.

  The level of 1,3-propanediol purity can be characterized in a number of different ways. For example, measuring the residual level of contaminating organic impurities is one useful measure. Biologically derived 1,3-propanediol may have a purity level of total organic contaminants of less than about 400 ppm; preferably about 300 ppm; and most preferably less than about 150 ppm. The term ppm total organic purity refers to parts-per-million levels of carbon-containing compounds (other than 1,3-propanediol) as measured by gas chromatography.

  Biologically derived 1,3-propanediol can also be characterized using many other parameters such as ultraviolet absorption at various wavelengths. Wavelengths of 220 nm, 240 nm, and 270 nm have been found useful in determining the purity level of the composition. Biologically derived 1,3-propanediol has a purity level with ultraviolet absorption of less than about 0.200 at 220 nm, and less than about 0.075 at 240 nm, and less than about 0.075 at 270 nm. obtain.

  Biologically derived 1,3-propanediol may have a b * color value (CIE L * a * b *) of less than about 0.15.

  The purity of the biologically derived 1,3-propanediol composition can also be assessed in a meaningful manner by measuring the level of peroxide. The biologically derived 1,3-propanediol composition can have a peroxide concentration of less than about 10 ppm.

  The above purity level parameters for biologically derived and purified 1,3-propanediol (using methods similar or comparable to those disclosed in US Patent Application No. 2005/0069997) are: It is conceivable to distinguish such compositions from 1,3-propanediol compositions prepared from chemically purified 1,3-propanediol derived from petroleum sources.

  Biologically produced 1,3-propanediol via fermentation is known and is described in US Pat. Nos. 5,686,276, 6,358,716, and 6,136,576. These are recombinantly engineered bacteria capable of synthesizing 1,3-propanediol during fermentation using an inexpensive environmentally friendly carbon source such as glucose or other sugars from plants A method of using is disclosed. These patents are specifically incorporated herein by reference. Biologically derived 1,3-propanediol is based on the use of a fermentation broth produced by genetically engineered E. coli, as disclosed in US Pat. No. 5,686,276. Can be obtained. Other single organisms or combinations of organisms may also be used to biologically produce 1,3-propanediol using organisms genetically engineered according to methods known to those skilled in the art. . “Fermentation” refers to a system that catalyzes a reaction between a substrate and other nutrients through the use of a biocatalyst to yield a product. A biocatalyst can be a whole organism, an isolated enzyme, or any combination or component thereof that is enzymatically active. Fermentation systems useful for producing and purifying biologically derived 1,3-propanediol are disclosed, for example, in published US patent application 2005/0069997, which is specifically incorporated herein by reference. Is done.

  Biologically derived 1,3-propanediol contains carbon from the atmosphere taken up by plants that constitutes the raw material for the production of biologically derived 1,3-propanediol. In this way, the biologically derived 1,3-propanediol contains only renewable carbon and no fossil fuel-based carbon or petroleum-based carbon. Therefore, the use of biologically derived 1,3-propanediol and its conjugated esters has less impact on the environment, and 1,3-propanediol eliminates the reduction of fossil fuels. The use of biologically derived 1,3-propanediol and its conjugated esters also does not make a net addition of carbon dioxide to the atmosphere and therefore does not contribute to greenhouse gas emissions. Thus, the present invention is more natural and may have less environmental impact than similar compositions containing petroleum-based glycols.

  Furthermore, as the purity of the biologically derived 1,3-propanediol utilized in the compositions described herein is higher than chemically synthesized pdo and other glycols, stimulation is increased. The risk of introducing impurities that may result is reduced by its use over commonly used glycols such as propylene glycol.

  In one embodiment of the invention, a composition comprising 1,3-propanediol and an ester of 1,3-propanediol is provided, wherein 1,3-propanediol is biologically derived. Biologically derived 1,3-propanediol in these compositions is at least 85% bio-based carbon, at least 95% bio-based, as assessed by ASTM-D6866 application, as described above. It can have a base carbon or 100% bio-based carbon.

  Biologically derived 1,3-propanediol samples were analyzed using ASTM method D6866-05. The results received from Iowa State University demonstrated that the sample was 100% biobased content. In a separate analysis, chemical or petroleum-based 1,3-propanediol (purchased from SHELL) was found to have a biobased content of 0%, as was also performed using the ASTM-D6866 method. It was issued. Propylene glycol (USP grade from ALDRICH) was found to have a biobased content of 0%.

  For example, it is contemplated by the present invention that other renewable or biologically derived glycols such as ethylene glycol or 1,2-propylene glycol, diethylene glycol, triethylene glycol can be used in the compositions of the present invention.

  The composition of the present invention is a combination of a biologically derived 1,3-propanediol and one or more biologically non-derived glycol components, eg, chemically synthesized 1,3-propanediol. There may be specific examples that may include: In such cases, it is difficult, if not impossible, to determine what percentage of the glycol composition is biologically derived, except by calculating the bio-based carbon content of the glycol component. obtain. In this regard, the use of 1,3-propanediol to form a 1,3-propanediol ester in the compositions of the present invention can be from at least about 1% biobased carbon content to 100% biobased. Can include any percentage up to and between the carbon content.

Biologically-derived 1,3-propanediol conjugate esters Biologically-derived 1,3-propanediol, an ester of “biological PDO” can be synthesized by contacting biological PDO with an organic acid. . The organic acid may be from any source, preferably from a biological source, or may be synthesized from a fossil source. Most preferably, the organic acid is derived from a natural source or is biologically derived having the chemical formula R ₁ —COOH. When in the substituent R ₁ , saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic, linear or branched, 1 to 40 chain length hydrocarbons, or salts or alkyl esters thereof It can be. The hydrocarbon chain may also contain one or more functional groups such as alkene groups, amide groups, amine groups, carbonyl groups, carboxylic acid groups, halide groups, hydroxyl groups, and the like. All esters produced with naturally occurring organic acids contain bio-based carbon. These naturally occurring organic acids, especially those produced by biological organisms, are classified as biological products, and the resulting esters or diesters can also be classified as biological products. Natural sources of such fatty acids include coconut oil, various animal tallows, lanolin, fish oil, beeswax, palm oil, peanut oil, olive oil, cottonseed oil, soybean oil, corn oil, rapeseed oil. Conventional fractionation and / or hydrolysis techniques can be used to obtain fatty acids from such materials, if necessary.

Suitable carboxylic acids to produce biologically derived esters of 1,3-propanediol generally include: (1) C, including monocarboxylic acids including formic acid and acetic acid. _1- C ₃ carbon; (2) fatty acids, eg fatty acids containing 4 or more carbon atoms; (3) saturated fatty acids, eg butyric acid, caproic acid, valeric acid, caprylic acid, capric acid, lauric acid, myristic acid Palmitic acid, stearic acid, arachidonic acid, and behenic acid; (4) unsaturated fatty acids such as oleic acid, linoleic acid, and uricic acid; (5) polyunsaturated fatty acids such as α-linolenic Acid, stearidonic acid (or moroctic acid), eicosatetraenoic acid, omega-6 fatty acid, arachidonic acid, and omega-3 fatty acid, eicosapentaenoic acid (Or timnodonic acid), docosapentaenoic acid (or crupanodonic acid), and docosahexaenoic acid (or cervonic acid); (6) hydroxy fatty acids such as 2-hydroxylinoleic acid and ricinoleic acid; phenylalkane fatty acids such as 11- Phenylundecanoic acid, 13-phenyltridecanoic acid, and 15-phenyltridecanoic acid; and (7) cyclohexyl fatty acids such as 11-cyclohexylundecanoic acid and 13-cyclohexyltridecanoic acid.

  The following acids and their salts or alkyl esters are particularly useful: acetic acid, butyric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, adipic acid, benzoic acid, caprylic acid, maleic acid, palmitic acid, Sebacic acid, arachidonic acid, erucic acid, palmitoleic acid, pentadecanoic acid, heptadecanoic acid, nondecanoic acid, octadectetraenoic acid, eicosatetraenoic acid, eicosapentaenoic acid, docasapentaenoic acid, tetracosapentaene Acid, tetrahexaenoic acid, docosahexaenoic acid, (α) -linolenic acid, docosahexaenoic acid, eicosapentaenoic acid, linoleic acid, arachidonic acid, oleic acid, erucic acid, formic acid, propionic acid, valeric acid, caproic acid, capric acid, Ronic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, tartaric acid, citric acid, salicylic acid, acetylsalicylic acid, pelargonic acid, behenic acid, serotic acid, margaric acid, montanic acid, mellicic acid, russell Acids, cellomelicic acid, gedaic acid, celloplastic undecylenic acid, ricinoleic acid, and eleostearic acid, and mixtures of such acids. A more preferred list of suitable organic acids are acetic acid, adipic acid, benzoic acid, maleic acid, sebacic acid, and mixtures of such acids. A more preferred list of suitable “fatty acids”, generally referred to as acids containing 8 to 40 carbons in carbon, useful in the present invention includes butyric acid, valeric acid, caproic acid, caprylic acid, pelargon Acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidonic acid, behenic acid, serotic acid, oleic acid, linoleic acid, linolenic acid, margaric acid, montanic acid, melissic acid, raschelic acid, cellomelic acid, Included are geda acid, celloplastic acid, and mixtures of such acids. Among these acids, these acids, and their salts and alkyl esters are most preferably stearic acid, lauric acid, palmitic acid, oleic acid, 2-ethylhexanoic acid, and 12-hydroxystearic acid, and A mixture of such acids.

  Esters produced using the described organic acids include all suitable conjugated monoesters and diesters of 1,3-propanediol. Some esters produced include in particular: propanediol distearate and monostearate, propanediol dilaurate and monolaurate, propanediol dioleate and monooleate, propanediol divalerate and mono Valerate, propanediol dicaprylate and monocaprylate, propanediol dimyristate and monomyristate, propanediol dipalmitate and monopalmitate, propanediol dibehenate and monobehenate, propanediol adipate, propanediol maleate, Propanediol dibenzoate, propanediol diacetate, and mixtures of all of these.

  In particular, the esters produced include: propanediol distearate and monostearate, propanediol dioleate and monooleate, propanediol dicaprylate and monocaprylate, propanediol dimyristate and monomyristate , And a mixture of all of these.

  In general, 1,3-propanediol, preferably in the presence of an inert gas, in the presence of a fatty acid, or a mixture of fatty acids, or a salt of a fatty acid, and one or more catalysts. Or, in the absence, they can be contacted and reacted at a temperature in the range of 25 ° C to 400 ° C.

  During contact, water forms and can be removed in an inert gas or under vacuum to drive the completion of the reaction. Any volatile by-products can be removed as well. When the reaction is complete, the heating is stopped and cooled.

  The catalyst can be removed by dissolving and removing, preferably in deionized water. If the catalyst can be removed by treatment in deionized water, the reaction mixture is treated with an aqueous acid or base solution to form a salt and the salt is removed by either washing or filtration.

  Preferably, for pharmaceutical applications, further purification to obtain high purity fatty acid esters is by dissolving in a solvent that dissolves fatty acid esters easily at higher temperatures and minimally at lower temperatures. As well as by recrystallization with or without additional solvent at low temperature.

  The catalyst can be an acid, by way of non-limiting example, sulfuric acid, or p-toluenesulfonic acid. The catalyst can also be a base, by way of non-limiting example, sodium hydroxide. The catalyst can be a salt, by way of non-limiting example, potassium acetate. The catalyst can also be an alkoxide, by way of non-limiting example, titanium tetraisopropoxide. The catalyst can also be a heterogeneous catalyst, such as, but not limited to, a zeolite, heteropoly acid, amberlist, or ion exchange resin. The catalyst can also be a metal salt, such as, but not limited to, tin chloride or copper chloride. The catalyst can also be an enzyme, such as an enzyme known in the art. The catalyst can also be an organic acid, for example, by way of non-limiting example, formic acid. Finally, the catalyst can also be an organometallic compound, as a non-limiting example, n-butyl stannic acid.

  This process can be carried out in the presence or absence of a solvent. If a solvent is not required to facilitate the production of fatty acid esters, the method is preferably carried out in the absence of a solvent.

This process can be carried out at atmospheric pressure or under vacuum or under pressurized conditions.
Reaction 1 (Diester)

Where R ₁ and R ₂ are hydrocarbons, preferably have a carbon chain length of from about 1 to about 40. Such hydrocarbons can be saturated or unsaturated, substituted or unsubstituted, linear or branched.
M is hydrogen, an alkali metal, or an alkyl group.
Reaction 2 (monoester)

Where R ₁ is a hydrocarbon, it preferably has a carbon chain length of about 1 to about 40. Such hydrocarbons can be saturated or unsaturated, substituted or unsubstituted, linear or branched. M is hydrogen, an alkali metal, or an alkyl group.

The composition according to the invention comprises one or more R ₁ selected from the group consisting of alkenes, amides, amines, carbonyls, carboxylic acids, halides, hydroxyl groups, ethers, alkyl ethers, sulfates, and ether sulfates. Includes esters with functional groups. These esters can have the formula R ₁ —C (═O) —O—CH ₂ —CH ₂ —CH ₂ —O—C (═O) —R ₂ , where both R ₁ and R ₂ are It is a straight or branched chain having a length of between about 1 and about 40 carbons. R ₁ and R ₂ represent one or more functional groups selected from the group consisting of alkenes, amides, amines, carbonyls, carboxylic acids, halides, hydroxyl groups, ethers, alkyl ethers, sulfates, and ether sulfates. Can have. In addition, R ₁ and R ₂ can be the same carbon chain in the case of diesters.

  Any molar ratio of diol to carboxylic acid or salt or ester thereof can be used. The preferred range of diol to carboxylic acid is about 1: 3 to about 2: 1. This ratio can be adjusted to shift the priority of the reaction from monoester production to diester production. In general, preference is given to the production of diesters slightly higher than the ratio of about 1: 2; on the other hand, preference is given to the production of monoesters in the ratio of about 1: 1. In general, if a diester product is desired beyond the monoester, the ratio of diol to dicarboxylic acid can range from 1.01: 2 to 1.1: 2; however, the monoester is desired A ratio range of about 1.0: 1 to about 2: 1 is used.

  The catalyst content for the reaction can be from 1 ppm to 60% by weight of the reaction mixture, preferably from 10 ppm to 10% by weight of the reaction mixture, more preferably from 50 ppm to 2%.

  Depending on the reaction conditions, this product may contain diesters, monoesters, or a combination of diesters and monoesters, and small proportions of unreacted acids and diols. Unreacted diol can be removed by washing with deionized water. Unreacted acid can be removed by washing with deionized water or an aqueous solution having a base, or during recrystallization.

  Any ester of 1,3-propanediol can be made or used in accordance with the present invention. Short, medium and long chain monoesters and diesters of 1,3-propanediol can be made. Specifically, acids containing between about 1 and about 36 carbons in the alkyl chain can be made. More specifically, the following monoesters and diesters can be made: propanediol distearate (monostearate and mixtures), propanediol dilaurate (monolaurates and mixtures), propanediol dioleate (monooleates and mixtures) Propanediol divalerate (monovalerate and mixtures), propanediol dicaprylate (monocaprylate and mixtures), propanediol dimyristate (monomyristates and mixtures), propanediol dipalmitate (monopalmitate and Mixture), propanediol dibehenate (monobehenate and mixture), propanediol adipate, propanediol maleate, propanediol dibenzoate, propanediol di Seteto.

  A composition comprising a biologically derived ester of 1,3-propanediol comprises a biobased carbon from a biologically derived 1,3-propanediol. Thus, these esters can have varying amounts of bio-based carbon, depending on which acid is used in the esterification process. The composition includes a carbon chain of the organic acid used to produce the ester, regardless of whether the ester is a diester or a monoester, and whether the organic acid comprises bio-based carbon or fossil fuel carbon. Depending on length, at least 3% bio-based carbon, at least 6% bio-based carbon, at least 10% bio-based carbon, at least 25% bio-based carbon, at least 50% bio-based carbon, at least 75% Or an ester with 100% bio-based carbon.

  These compositions comprising an ester of 1,3-propanediol provide a biologically produced 1,3-propanediol; contacting 1,3-propanediol with an organic acid, It can be produced by producing an ester; and recovering the ester. The provided 1,3-propanediol can have at least 95% bio-based carbon, or 100% bio-based carbon. In addition, the biologically produced 1,3-propanediol provided for the method can have at least one of the following features: 1) less than about 0.200 at 220 nm, and 250 nm Less than about 0.075 at 275 nm and less than about 0.075 at 275 nm; 2) L * a * b * “b *” color value less than about 0.15 and less than about 0.075 at 270 nm 3) a peroxide composition of less than about 10 ppm; and 4) a concentration of total organic impurities of less than about 400 ppm.

  The ester also provides 1,3-propanediol having at least 90% biobased carbon; contacting 1,3-propanediol with an organic acid to form an ester; and recovering the ester, Can be produced. The step of bringing 1,3-propanediol into contact with an acid can be performed in the presence of a catalyst for promoting an esterification reaction, and the catalyst includes an acid, a base, a salt, an alkoxide, a heterogeneous catalyst, and a metal salt. Can be classified as one or more members of enzymes, organic acids, and organometallic compounds. Specifically, the catalyst is sulfuric acid or p-toluenesulfonic acid, sodium hydroxide, potassium acetate, titanium tetraisopropoxide, zeolite, heteropoly acid, amberlist, ion exchange resin, tin chloride, copper chloride, formic acid. Or n-butyl stannic acid.

  The 1,3-propanediol esters described herein are useful in many applications. Esters of 1,3-propanediol are used as personalizers, cosmetics, food products, surfactants and soaps as plasticizers in polymer products and in the extraction process and as solvents or diluents for extraction solutions. Useful in products.

  Conjugated esters of 1,3-propanediol are emulsifiers, brighteners, surfactants, gelling agents, structurants for use in personal compositions such as liquid hand soaps, shampoos, and body surfactants. Suitable as a thickener, opacifier, in a non-limiting manner. The esters described herein are particularly desirable as ingredients in liquid soap, shampoo, and body surfactant formulations. This is because they provide the intended functionality and can be produced from biologically derived compounds.

  Esters of 1,3-propanediol are also useful as emollients and as active ingredients in personal care products and cosmetics. In other applications, such esters are useful in the delivery, application, or effectiveness of personal care products and cosmetics. The ester acts as an additive or adjuvant when used to improve product delivery, application, or effectiveness. Specifically, in a non-limiting manner, these esters are moisturizers, opacifiers, brighteners, gelling agents, emulsifiers, surfactants, structurants, thickeners for cosmetic and personal care products. , Admixtures, or solvents.

  1,3-propanediol esters can also be included in surfactant compositions for various purposes. Depending on the particular formulation, these esters can be hydrotropes, stabilizers, binders, emulsifiers, modifiers, brighteners, surfactants, gelling agents, structuring agents, thickeners, and Functions as an opacifier.

  Other ingredients used with 1,3-propanediol in surfactants and soaps include: diamines that are useful in improving cleaning performance; surfactants that improve cleaning performance; physical And glycols that enhance enzymatic stability; water-directing agents that act as phase stabilizers; foam stabilizers that expand foam volume and duration; builders that assist the action of surfactants; enzymes that improve cleaning performance; Buffers that work to regulate; alkaline inorganic salts that support surfactant action; perfumes that remove iron and manganese.

  Some suitable surfactant compositions include liquid soaps, liquid surfactants, household detergent products, and industrial detergent products. Some specific surfactants that are suitable for use with 1,3-propanediol esters include hand dishwashing surfactants, machine wash surfactants, solid surfactants, solid laundry surfactants , Liquid laundry surfactants, light liquid surfactants, heavy liquid surfactants, organic and inorganic clothing softeners, laundry soaps, and car wash surfactants.

  The 1,3-propanediol esters provided herein are also effective as plasticizers in various polymers. The polymer composition can be made into films including both molded items, foams, cast films and biaxially oriented films using conventional equipment. The steps involved are typically dry blending of the polymer, melt blending of the polymer, pelleting by extruding the polymer (including other shapes such as flakes), remelting the pellet, extruding the pellet through the die At a temperature in the range of about 160 ° C to about 300 ° C.

  Polyvinyl chloride (PVC) is a generally plasticized polymer. Highly flexible PVC is used in a wide range of applications such as floor tiles, sheet flooring, carpet lining, and in different medical devices. Over 90% of the plasticizer is used in the PVC industry. Without the plasticizer, PVC has a very limited application as a polymer material.

  1,3-propanediol esters can also be used in other polymers including acrylic polymers. These are mostly acrylic ester polymers and methacrylic ester polymers. Highly flexible coatings are produced using acrylic with a plasticizer. The compatibility of the plasticizer with the acrylic is up to about 10% by weight, but higher compatibility can be achieved for low molecular weight plasticizers. The paper, “Influence of the Glycol Component in Dibenzoate Plasticizers on the Properties of the Plasticized PVC Films” Appl. Polym. Sci. , Vol. 97, 822-824 (2005) discloses the application of a chemically produced ester dibenzoate of 1,3-propanediol as a plasticizer in PVC applications. According to these results, chemically produced 1,3-propanediol dibenzoate exhibits acceptable or moderate plasticizer properties, whereas chemically derived 1,3-propane. The extraction results for plasticized PVC film samples using diol dibenzoate show excellent properties. These films exhibited excellent solvent resistance against nonpolar liquids (motor oil and gasoline) and also against water and ethanol.

  1,3-propanediol alginate is useful as an additive for beer. 1,3-propanediol alginate esters improve foam performance, increase foam adhesion ability, and improve beer appearance. 1,3-propanediol alginate esters weaken the effects of some ingredients that can extinguish beer foam. 1,3-propanediol alginate ester also increases the lifetime of the foam and makes the foam better.

  In the dairy industry, 1,3-propanediol alginate esters can be used to improve the texture and taste of yogurt. These characteristics are maintained even in products with a low content of milk solids. 1,3-propanediol alginate esters can effectively prevent the product from forming a rough surface and provide a smooth and glossy appearance. 1,3-propanediol alginate ester can be thoroughly mixed with other additives and can be used in a wide pH range. Gentle mixing can evenly mix the 1,3-propanediol alginate ester into yogurt. 1,3-propanediol alginate ester is stable in the heating process and can be used as a stabilizer and an emulsifier.

  Some specific uses of 1,3-propanediol alginate esters in food products include:

1. As a stabilizer in frozen dairy desserts, fruit and ice confectionery, and sugar coatings at levels not exceeding 0.5 weight percent of the final product.

2. As an emulsifier, flavor, adjuvant, stabilizer, or thickener in baked products at a level not exceeding 0.5 weight percent of the final product.

3. As an emulsifier, stabilizer, or thickener in cheese at a level not exceeding 0.9 weight percent of the final product.

4). As an emulsifier, stabilizer, or thickener in fats and oils at a level not exceeding 1.1 weight percent of the final product.

5. As an emulsifier, stabilizer, or thickener in gelatin and purines at a level not exceeding 0.6 weight percent of the final product.

6). As an emulsifier, stabilizer, or thickener in gravy and sweet sauce at a level not exceeding 0.5 weight percent of the final product.

7). As a stabilizer in jams and jellies at a level not exceeding 0.4 weight percent of the final product.

8). As an emulsifier, stabilizer or thickener in spices and condiments at a level not exceeding 0.6 weight percent of the final product.

9. As a flavor adjuvant or adjuvant in seasonings and flavors at a level not exceeding 1.7 weight percent of the final product.

10. Where applicable, as an emulsifier, flavor adjuvant, formulation aid, stabilizer or thickener, or surfactant in other foods at a level not exceeding 0.3 weight percent of the final product.

  The table below shows the classification of foods in which 1,3-propanediol alginate esters can be used, and the function of 1,3-propanediol alginate esters in these food compositions, as well as 1, A list of approximate upper limits approved by the FDA for the amount by weight of the alginate ester of 3-propanediol is provided.

  The following table provides a list of approximate upper limits for foods that can be used other than the 1,3-propanediol alginate ester, as well as the amount by weight of the 1,3-propanediol alginate ester in the food composition.

  A “food composition” includes a food or food ingredient comprising one or more ingredients. In addition, food compositions include human food, substances that transfer food from articles in contact with food, beverages, pet food, and animal food compositions.

  “Ingredient” includes any ingredient that can be used in a food composition. Ingredients must be of appropriate food grade; prepared and handled as food ingredients; and the amount of ingredients added to the food achieves the intended physical, nutritional, or other technical effect in the food It is preferable not to exceed the amount reasonably required for this purpose.

  The food composition of the present invention comprises 0.0001% to 20% 1,3-propanediol ester by weight, and more preferably about 0.1% to about 10% 1,3-propanediol ester. obtain. A typical food composition formulation of the present invention may comprise 0.5% to 5% 1,3-propanediol ester.

  In the food composition of the present invention, 1,3-propanediol ester is a dough reinforcing agent, emulsifier, emulsifier salt, fragrance, fragrance adjuvant, blending aid, processing aid, solvent, medium, stabilizer, thickener, It can be a surfactant, texture agent, gelling agent, gelatinizing agent, lubricant, binder, foaming agent, or antifoaming agent.

  A non-limiting list of food compositions of the present invention comprising 1,3-propanediol ester includes the following: fruit filling for pastries containing up to about 10% 1,3-propanediol ester by weight; Beverage whitener containing up to about 4% 1,3-propanediol ester; cereal and starch-based desserts containing up to about 4% 1,3-propanediol ester by weight (eg rice pudding, tapioca pudding) A predominantly oil-in-water fat emulsion containing a mixture and / or flavoring product based on a fat emulsion comprising up to about 5% by weight of 1,3-propanediol ester; up to about 4% by weight of 1,3- Hard, other than food classification 05.1, 05.3, and 05.4, including propanediol esters Confectionery including soft candy, nougat, etc .; chewing gum containing up to about 4% by weight of 1,3-propanediol ester; vegetable oils and fats containing up to about 4% by weight of 1,3-propanediol ester; Blend of butter and margarine containing up to 4% 1,3-propanediol ester; nutritional formulation for slimming purposes and weight loss containing up to about 3% 1,3-propanediol ester by weight; Cream analogs containing up to 2% 1,3-propanediol ester; nutritional foods intended for special medical purposes containing up to about 2% 1,3-propanediol ester by weight (food category 13. Emulsions containing less than 80% fat containing up to about 2% by weight of 1,3-propanediol ester) Lard, tallow, fish oil and other animal oils containing up to about 1.5% by weight of 1,3-propanediol ester; bakery products containing up to about 1% by weight of 1,3-propanediol ester Dairy based beverages, flavored beverages and / or fermented beverages containing up to about 1% by weight of 1,3-propanediol ester (eg chocolate milk, cocoa, eggnog, drinking yogurt, whey based beverages); Water-based flavored beverages including “sports”, “energy” or “electrolyte” beverages and certain beverages, containing up to about 0.5% by weight of 1,3-propanediol ester; about 0.5% by weight Milk and cream powder analogs containing up to 1,3-propanediol ester; up to about 0.5% by weight 1,3-propanediol ester Fruit-based desserts, including fruit-flavored water-based desserts containing tellurium; up to about 0.5% by weight of 1,3-propanediol ester, decorations (eg for fine bakery wear), toppings ( Non-fruit) and sweet sauce; egg-based dessert containing up to about 0.5% by weight of 1,3-propanediol ester; margarine containing up to about 0.5% by weight of 1,3-propanediol ester And similar products; including up to about 0.5% by weight of 1,3-propanediol ester, including sorbet and sorbet); edible ice; up to about 0.5% by weight of 1,3-propanediol ester Vegetables other than food category 04.2.2.5, including mushrooms and fungi, roots and tubers, beans and beans Plants, and aloe vera), seaweed, and nuts and seed pulps and regenerated products (eg, plant desserts and sauces, plant candy); cocoa mixtures containing up to about 0.5% by weight of 1,3-propanediol ester (Powder) and cocoa mass / cake; other sugars and syrups containing up to about 0.5% by weight of 1,3-propanediol ester (eg, xylose, maple syrup, sugar topping); about 0.1 by weight Fat-based desserts excluding dairy-based dessert products other than food category 01.7, containing up to 1% 1,3-propanediol esters; up to about 0.05% 1,3-propanediol esters by weight A fruit preparation comprising pulp, puree, fruit topping, and coconut milk.

  In addition, these esters are useful in a variety of industrial applications. The following table lists several markets where there are suitable applications for the 1,3-propanediol esters described in this invention. The use of esters in these applications is briefly described and an appropriate range of weight percent for esters is provided for each market. In each of the applications listed in the table below, esters of 1,3-propanediol can optionally be used with 1,3-propanediol.

Application for 1,3-propanediol ester

  Abbreviations have the following meanings: “min” means minutes, “seconds” means seconds, “h” means hours, “μL” means microliters. Means "mL" means milliliter, "L" means liter, "nm" means nanometer, "mm" means millimeter, "cm" means centimeter, “Μm” means micrometer, “mM” means millimolar, “M” means molar, “mmol” means millimolar, “μmole” means micromolar, “ “g” means grams, “μg” means micrograms, “mg” means milligrams, “g” means gravity constant, “rpm” means rotation per minute, “SEM” means standard error of the mean, “volume%” It means percent by volume, and "NMR" means nuclear magnetic resonance.

  Further, the meanings of the abbreviations used are as follows: “wt%” means wt%; “qs” means proper amount; “EDTA” means ethylenediaminetetraacetic acid; Means degrees Celsius; “° F.” is Fahrenheit temperature, “Bio-PDO” means biologically derived 1,3-propanediol; “ppm” is parts per million; “AU” is an absorption unit; “nm” is a nanometer; “GC” is a gas chromatograph; “APHA” is the American Public Health Association; “cps” is a centipoise. Yes; “f / t” is freeze / thaw; “mPa · s” is millipascal second; “DI” is deionized.

  The invention is further defined in the following examples. It should be understood that these examples are given by way of illustration only, while illustrating preferred embodiments of the present invention. From the above discussion and these examples, those skilled in the art can ascertain the essential features of the invention and make various changes and modifications to the invention without departing from the spirit and scope of the invention. The present invention can be adapted to various applications and conditions.

General Methods Standard recombinant DNA and molecular cloning techniques used in the examples are well known in the art and are described in Sambrook, J. et al. , Fritsch, E .; F. and Maniatis, T .; , Molecular Cloning: A Laboratory Manual, Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N .; Y. , 1989, by T. et al. J. et al. Silhavy, M .; L. Bennan, and L.M. W. Enquist, Experiments with Gene Fusions, Cold Spring Harbor Laboratory, Cold Spring Harbor, N .; Y. , 1984, and Ausubel, F .; M.M. Et al, Current Protocols in Molecular Biology, Green Publishing Assoc. and Wiley-Interscience, N .; Y. 1987.

  Suitable materials and methods for maintaining and growing bacterial cultures are also well known in the art. Techniques suitable for use in the following examples are described in Manual of Methods for General Bacteriology, Phillip Gerhardt, R .; G. E. Murray, Ralph N .; Costilow, Eugene W. Nester, Willis A. Wood, Noel R.D. Krieg and G. Briggs Phillips, eds. , American Society for Microbiology, Washington, D .; C. 1994, Thomas D .; Block in Biotechnology: A Textbook of Industrial Microbiology, Second Edition, Sinauer Associates, Inc. Sunderland, MA. , 1989.

  All reagents, restriction enzymes, and materials used for bacterial cell growth and maintenance, unless otherwise specified, are Aldrich Chemicals (Milwaukee, WI), BD Diagnostics Systems (Sparks, MD), Life Technologies (Rockville, MD). Or obtained from Sigma Chemical Company (St. Louis, Mo.).

  Glycerol used for the production of 1,3-propanediol is described in J. Org. T.A. Obtained from Baker Glycerin USP grade, lot J25608 and G19657.

Differential Scanning Calorimeter: DSC thermograms were recorded using a Universal V3 1A TA under a constant flow of nitrogen using a heating and cooling rate of 10 ° C./min.

NMR: 1H NMR spectra were recorded on a Bruker DRX 500 using XWIN NMR version 3.5 software. Data was acquired using a 90 degree pulse (p1) and a 30 second recycle delay (d1). The sample was dissolved in deuterium-substituted chloroform, and chloroform without deuterium substitution was used as an internal standard.

Bio-PDO Isolation and Identification Conversion of glycerol to bio-PDO was monitored by HPLC. Analysis was performed using standard techniques and materials available to those skilled in the art of chromatography. One suitable method utilized a Waters Maxima 820 HPLC system using UV (210 nm) and RI detection. A Shodex SH-1011 column (8 mm x 300 mm) equipped with a Shodex SH-1011P precolumn (6 mm x 50 mm) using 0.01N H2SO4 as the mobile phase at a flow rate of 0.5 mL / min with a temperature controlled at 50 ° C. , Purchased from Waters, Milford, MA). Where quantitative analysis was desired, samples were prepared with a known amount of trimethylacetic acid as an external standard. Typically, the retention times of glycerol (RI detection), 1,3-propanediol (RI detection), and trimethylacetic acid (UV and RI detection) are 20.67 minutes, 26.08 minutes, and 35, respectively. 0.03 minutes.

  Bio-PDO production was confirmed by GC / MS. The analysis was performed using standard techniques and materials available to those skilled in the art of GC / MS. One suitable method is a Hewlett Packard 5890 Series II gas chromatograph coupled to a Hewlett Packard 5971 series mass selective detector (EI) and an HP-INNOWax column (30 m long, 0.25 mm ID, 0.25 micron film thickness). used. The retention time and mass spectrum of 1,3-propanediol generated from glycerol were compared to that of a reliable 1,3-propanediol (m / e: 57,58).

Production of bio-based monoesters and diesters from bio-produced 1,3-propanediol Bio-monoesters and diesters of 1,3-propanediol may be produced by combining bio-PDO with organic acids. The combination is preformed under dry conditions under heating and with long agitation with the selected catalyst. The ratio of monoester to diester varies according to the molar ratio of acid to biological PDO and the choice of catalyst.

The production of the ester was confirmed using ¹ H nuclear magnetic resonance. The analysis was performed using standard techniques and materials available to those skilled in the field of ¹ H NMR.

Proton nuclear magnetic resonance ( ¹ H NMR) spectroscopy is a powerful method used in determining the structure of known organic compounds. This provides information related to the number of different types of hydrogen present in the molecule, the electronic environment of the different types of hydrogen, and the number of “adjacent” hydrogens the hydrogen has.

Hydrogen bonded to carbon bonded to electron withdrawing groups tends to resonate at higher frequencies from common NMR standards, TMS, trimethylsilane. The position at which a particular hydrogen atom resonates compared to TMS is called its chemical shift (δ). Typical chemical shifts of fatty acids are as follows:
For the terminal CH ₃
δ = 0.88
_{(-CH 2 -C H 2 -CH 2} ), the methylene group of the _{(C H 2 -CH 2 -C =} O) and _{(O-CH 2 -C H 2} -CH 2 -O), respectively,
δ = 1.26, 1.61 and 1.97.
Δ = 2.28 for an methylene group (C H ₂ -C═O) adjacent to the ester
For the ester (C (═O) —O— CH ₂ —) δ = 4.15
Proton NMR can distinguish the proton corresponding to the terminal group (C H ₂ —OH) (δ = 3.7) from that of the intermediate ester group (C H ₂ —O—C (═O) —). (For diesters and monoesters, δ = 4.15 and 4.24, respectively), so it is possible to identify the ester and monitor the reaction by comparing the integrated area of these two peaks it can.

Example 1
Conversion of D-glucose to 1,3-propanediol under fermentation conditions pneumoniae dha regulon cosmid pKP1 or pKP2; The E. coli strain ECL707 containing the pneumoniae pdu operon pKP4, or the Supercos vector alone, was grown in a 5L Applikon fermentor for the production of 1,3-propanediol from glucose.

The medium used was 50-100 mM potassium phosphate buffer, pH 7.5, 40 mM (NH ₄ ) ₂ SO ₄ , 0.1% (w / v) yeast extract, 10 μM CoCl ₂ , 6.5 μM CuCl ₂ , 100 μM FeCl ₃ , 18 μM FeSO ₄ , 5 μM H ₃ BO ₃ , 50 μM MnCl ₂ , 0.1 μM Na ₂ MoO ₄ , 25 μM ZnCl ₂ , 0.82 mM MgSO ₄ , 0.9 mM CaCl ₂ , and 10-20 g / L glucose Including. Supply additional glucose and maintain excess glucose in excess. The temperature is controlled at 37 ° C. and the pH is controlled at 7.5 with 5N KOH or NaOH. Appropriate antibiotics are included for plasmid maintenance. For anaerobic fermentation, 0.1 vvm nitrogen is sparged through the reactor; if the dO set point is 5%, 1 vvm air is sparged through the reactor and the medium is supplemented with vitamin B12.

  The titer (g / L) of 1,3-propanediol is in the range of 8.1 to 10.9. The yield of bio-PDO (g / g) ranges from 4% to 17%.

Example 2
Purification of biological source 1,3-propanediol Published US Patent Application No. 2005/0069997 discloses 1,3-propanediol from a fermentation broth of cultured E. coli bioengineered to synthesize 1,3-propanediol from sugar. A method for purifying propanediol is disclosed. The basic method involves filtration, ion exchange, and distillation of the fermentation broth product stream, and preferably involves chemical reduction of the product during the distillation procedure.

  The 1,3-propanediol produced as shown in Example 1 was purified by a multi-step process including broth clarification, rotary evaporation, anion exchange, and multiple distillation of the supernatant.

  At the end of the fermentation, the broth was clarified using a combination of centrifugation and membrane filtration for cell separation followed by ultrafiltration through a 1000 MV membrane. The clarified broth was processed with a large rotary evaporator. Approximately 46 pounds of feed (21,000 grams) was processed into a concentrated syrup. A 60 ml portion of the syrup was placed in a distillation pot of a 1 "diameter distillation column. Distillation was performed in a 25 inch mercury vacuum. During the distillation, a reflux ratio of about 1 was used. A cut was taken and further processed in the center The material was diluted with an equal volume of water and placed in an anion exchange column (mixed bed, 80 grams of NM-60 resin) which was washed with water. Fractions were collected every 9 minutes, and odd fractions were analyzed and fractions 3 to 9 contained 3 G. Fractions containing 3 G were collected and subjected to microdistillation. Several grams of pure 1,3-propanediol monomer was recovered (which was polymerized into monoesters and diesters according to the methods described in Examples 2-8).

Example 3
Production of propanediol distearate using p-toluenesulfonic acid as catalyst. To prepare propanediol distearate from biogenic 1,3-propanediol and stearic acid, biogenic 1,3-propanediol was carried out Purified using the method as in Examples 1 and 2. 2.58 g (0.033 mol) biogenic 1,3-propanediol, 19.45 g (0.065 mol) stearic acid (Aldrich, 95%) and 0.2125 g (0.001 mol) p- Toluenesulfonic acid (Aldrich 98.5%) was charged into a glass reactor equipped with a mechanical stirrer, and dry nitrogen gas was passed through the reactor to remove air and moisture for 15 minutes. The reaction temperature was then raised to 100 ° C. while stirring the reaction mixture under a stream of nitrogen and continued for 210 minutes.

  After completion of the reaction, the reaction mixture was cooled to about 35 ° C. and the product was transferred to a beaker. The product was purified by adding 100 mL of water and stirring thoroughly at 45-60 ° C. to form an emulsion in 15 minutes. The mixture was cooled and the solid propanediol distearate was separated by filtration.

As shown in FIG. 1, the product has a ¹ H NMR (nuclear magnetic resonance) spectrum (CDCl ₃ (deuterium-substituted chloroform)): δ = 0.88 (t, C H ₃ —CH ₂ , 6H), 1 _{.26 (t, CH 2 -C H} 2 -CH 2, 28H), 1.61 (t, C H 2 -CH 2 -C = O, 4H), 1.97 (t, -O-CH 2 - _{C H 2 -CH 2 -O, 2H} ), 2.28 (t, C H 2 -C = O, 4H), 4.15 (t, C (= O) -O-C H 2 -4H) and Characterized by DSC (Tm = 66.4 ° C. and Tc = 54.7 ° C.).

Example 4
Characterization of purity of biologically derived 1,3-propanediol In Table 1 below, biologically derived 1,3-propanediol (described in published US patent application 2005/0069997). Production and purification) ("Bio-PDO") in two purity embodiments, in two purity embodiments, two separate commercially obtained preparations of chemically produced 1,3-propanediol ( Compare with sources A and B).

Table 1

  Exemplary profiles of purity aspects for biologically produced 1,3-propanediol samples purified by the method disclosed in published US Patent Application No. 2005/0069997 are shown in Table 2 below. provide.

Table 2

  The unit ppm of total organic impurities means one millionth of the total organic compounds in the final preparation other than 1,3-propanediol as measured by gas chromatography using a flame ionization detector. Results are reported by peak area. Flame ionization detectors are not sensitive to water, so the total purity divided by the sum of all area percent (including 1,3-propanediol), all organics that are not 1,3-propanediol It is the sum of peaks (area%). The term “organic material” refers to impurities containing carbon.

  The table shows that the purification method disclosed is highly pure biologically derived 1, when compared to a commercially obtained preparation of 1,3-propanediol that is chemically produced. It shows providing 3-propanediol.

Example 5
Production of propanediol distearate using p-toluenesulfonic acid as catalyst 39.61 g (0.1333 mol) stearic acid (Aldrich, 95%), 5.05 g (0.066 mol) biogenic 1, 3-propanediol (Bio-PDO) and 0.46 g (0.0024 mol) of p-toluenesulfonic acid were charged into a glass reactor equipped with a mechanical stirrer, and dry nitrogen gas was passed through the reactor. Air and moisture were removed for minutes. The reaction temperature was then raised to 100 ° C. while stirring the reaction mixture under a stream of nitrogen. When the reaction temperature reached 100 ° C., the nitrogen flow was stopped and a low vacuum was applied to remove by-products. The reaction was continued for 2 hours. The vacuum was stopped and the product was cooled under a stream of nitrogen.

  The product was purified as described in Example 3 and recrystallized as described in Example 4.

The product was analyzed by ¹ H NMR spectrum (CDCl ₃ ): δ = 0.88 (t, CH ₃ —CH ₂ , 6H), 1.26 (t, CH ₂ —CH ₂ —CH ₂ , 28H), 1. _{61 (t, CH 2 -CH 2} -C = O, 4H), 1.97 (t, -O-CH 2 -CH 2 -CH 2 -O, 2H), 2.28 (t, CH 2 -C = O, 4H), was characterized by 4.15 (t, C (= O ) -O-CH 2 -4H). FIG. 4 shows a graph of these data.

Example 6
Production of propanediol monostearate and propanediol distearate using tin chloride as catalyst 72.06 g (0.243 mol) of stearic acid (Aldrich, 95%), 9.60 g (0.126 mol) of 1 , 3-propanediol, and 0.25 g of SnCl2 (Aldrich, 98%) were charged into a glass reactor equipped with a mechanical stirrer, and dry nitrogen gas was passed through the reactor to remove air and moisture for 15 minutes. . The reaction temperature was then raised to 100 ° C. while stirring the reaction mixture under a stream of nitrogen and continued for 240 minutes.

  After completion of the reaction, the reaction mixture was cooled and analyzed by NMR. The product contained 39 mol% propanediol monostearate, 19 mol% propanediol distearate, and 42 mol% 1,3-propanediol.

1H NMR spectrum (CDCl ₃ ): δ = 0.88 (t, CH ₃ —CH ₂ ), 1.27 (t, CH ₂ —CH ₂ —CH ₂ ), 1.63 (t, CH ₂ —CH ₂₎ -C = O), 1.82,1.87, and _{1.96 (t, -O-CH 2} -CH 2 -CH 2 -O,), 2.31 (t, CH 2 -C = O, ), 3.69 and 3.86 (t, HO—CH ₂ —CH ₂ —), 4.15 and 4.21 (t, C (═O) —O—CH ₂ —). FIG. 5 shows a graph of these data.

Example 7
Production of propanediol monostearate and propanediol distearate using titanium tetraisopropoxide as catalyst 35.51 g (0.119 mol) stearic acid (Aldrich, 95%), 9.55 g (0.125 mol) ) Of 1,3-propanediol and 0.01 g of Ti (OC3H7) 4 (Aldrich, 99.99%) were charged into a glass reactor equipped with a mechanical stirrer, and dry nitrogen gas was passed through the reactor. Air and moisture were removed for 15 minutes. The reaction temperature was then raised to 170 ° C. while stirring the reaction mixture under a stream of nitrogen and continued for 240 minutes. The reaction was then continued for an additional 30 minutes under vacuum. The vacuum was stopped and the product was cooled under a stream of nitrogen and analyzed by NMR.

  The product had 36 mol% propanediol monostearate and 64 mol% propanediol distearate.

¹ H NMR spectrum (CDCl ₃ ): δ = 0.88 (t, CH ₃ —CH ₂ ), 1.27 (t, CH ₂ —CH ₂ —CH ₂ ), 1.63 (t, CH ₂ —CH ₂ -C = O), 1.87 and _{1.96 (t, -O-CH 2} -CH 2 -CH 2 -O,), 2.31 (t, CH 2 -C = O,), 3. _{70 (t, HO-CH 2} -CH 2 -), 4.15 and 4.24 (t, C (= O ) -O-CH 2 -). FIG. 6 shows a graph of these data.

Example 8
Production of propanediol monostearate and propanediol distearate using potassium acetate as catalyst 39.72 g (0.133 mol) of stearic acid (Aldrich, 95%), 10.12 g (0.133 mol) of organism Origin 1,3-propanediol (Bio-PDO) and 2.47 g of potassium acetate (Aldrich, 99%) were charged into a glass reactor equipped with a mechanical stirrer and flushed with dry nitrogen gas, 15 Air and moisture were removed for minutes.

  The reaction temperature was then raised to 130 ° C. while stirring the reaction mixture under a stream of nitrogen. The reaction was continued for 4 hours under a stream of nitrogen. The nitrogen flow was then stopped and a vacuum was applied for 10 minutes before the reaction was stopped. The resulting product was analyzed without further purification.

  NMR analysis confirmed that the product contained 64.7 mol% propanediol monostearate, 9.7 mol% propanediol distearate, and 25.6 mol% 1,3-propanediol. did.

¹ H NMR spectrum (CDCl ₃ ): δ = 0.88 (t, CH ₃ —CH ₂ ), 1.27 (t, CH ₂ —CH ₂ —CH ₂ ), 1.63 (t, CH ₂ —CH ₂ -C = O), 1.82,1.87 and _{1.96 (t, -O-CH 2} -CH 2 -CH 2 -O,), 2.31 (t, CH 2 -C = O, ), 3.70 and 3.86 (t, HO—CH ₂ —CH ₂ —), 4.15 and 4.24 (t, C (═O) —O—CH ₂ —). FIG. 7 shows a graph of these data.

Example 9
Propanediol dilaurate production using p-toluenesulfonic acid as catalyst 50.2 g (0.246 mol) lauric acid (Aldrich, 98%), 9.35 g (0.123 mol) biogenic 1,3- Propanediol (Bio-PDO) and 0.6 g of p-toluenesulfonic acid (Aldrich, 98.5%) were charged into a glass reactor equipped with a mechanical stirrer, and dry nitrogen gas was passed through the reactor. Air and moisture were removed for minutes.

  The reaction temperature was then raised to 130 ° C. while stirring the reaction mixture under a stream of nitrogen. The reaction was continued for 4 hours under a stream of nitrogen. After completion of the reaction, the product was cooled and 90 mL of 0.5 wt% aqueous sodium hydroxide was added and stirred at 40-50 ° C. for 10 minutes. The product was then filtered, washed thoroughly with deionized water and dried.

  NMR analysis confirmed that the product contained 99.2 mol% propanediol dilaurate.

¹ H NMR spectrum (CDCl ₃ ): δ = 0.88 (t, CH ₃ —CH ₂ ), 1.27 (t, CH ₂ —CH ₂ —CH ₂ ), 1.63 (t, CH ₂ —CH _{2 -C = O), 1.96 (} t, -O-CH 2 -CH 2 -CH 2 -O,), 2.28 (t, CH 2 -C = O,), 4.15 (t, _{C (= O) -O-CH} 2 -).

Example 10
Propanediol dioleate production using p-toluenesulfonic acid as catalyst 51.7 g (0.164 mol) oleic acid (Aldrich, 90%), 6.26 g (0.082 mol) biogenic 1, 3-Propanediol (Bio-PDO) and 0.6 g of p-toluenesulfonic acid (Aldrich, 98.5%) were charged into a glass reactor equipped with a mechanical stirrer, and dry nitrogen gas was passed through the reactor. Removed air and moisture for 15 minutes.

  The reaction temperature was then raised to 130 ° C. while stirring the reaction mixture under a stream of nitrogen. The reaction was continued for 4 hours under a stream of nitrogen. After completion of the reaction, the product was cooled and 90 mL of 0.5 wt% aqueous sodium hydroxide was added and stirred at 40-50 ° C. for 10 minutes.

  The reaction was transferred to a separatory funnel and 500 mL of deionized water was added, causing the mixture to form two separate layers. The aqueous phase was removed.

  An additional 500 mL of deionized water was added, the solution was mixed, and an aqueous layer was present after two distinct layers formed. This process was repeated once more.

  NMR analysis confirmed that the product contained 99.2 mol% propanediol dilaurate.

¹ H NMR spectrum (CDCl ₃ ): δ = 0.88 (t, CH ₃ —CH ₂ ), 1.27 and 1.30 (t, CH ₂ —CH ₂ —CH ₂ ), 1.63 (t, _{CH 2 -CH 2 -C = O)} , 1.96 (t, -O-CH 2 -CH 2 -CH 2 -O,), 2.28 (t, CH 2 -C = O,), 4. _{15 (t, C (= O} ) -O-CH 2 -), 5.35 (m CH 2 -CH = CH-CH 2).

Example 11
Production of propanediol distearate using p-toluenesulfonic acid as catalyst The biogenic 1,3-propanediol is described herein, specifically as described in Examples 1 and 2. It was prepared as follows. 5.2 g (0.068 mol) of biogenic 1,3-propanediol, 38.9 g (0.13 mol) of stearic acid (Aldrich, 95%) and 0.425 g (0.002 mol) of p- Toluenesulfonic acid (Aldrich 98.5%) was charged into a glass reactor equipped with a mechanical stirrer, and dry nitrogen gas was passed through the reactor to remove air and moisture for 15 minutes. The reaction temperature was then raised to 130 ° C. while stirring the reaction mixture under a stream of nitrogen and continued at 130 ° C. for 195 minutes.

  The product was purified as described in Example 3. The product was further purified by recrystallization by dissolving in chloroform and adding acetone at 15 ° C. The recrystallized product was filtered and dried.

The product was analyzed by ¹ H NMR spectrum (CDCl ₃ ): δ = 0.88 (t, CH ₃ —CH ₂ , 6H), 1.26 (t, CH ₂ —CH ₂ —CH ₂ , 28H), 1. _{61 (t, CH 2 -CH 2} -C = O, 4H), 1.97 (t, -O-CH 2 -CH 2 -CH 2 -O, 2H), 2.28 (t, CH 2 -C = O, 4H), was characterized by 4.15 (t, C (= O ) -O-CH 2 -4H).

  Although the invention has been described and described herein with reference to specific embodiments, it is not intended to limit the invention to the details shown. Rather, various modifications may be made in the details within the scope and extent of equivalents of the claims and without departing from the invention.

Example 12
Antimicrobial detergent composition

  Compositions for antimicrobial detergents are prepared by combining the above ingredients in amounts within the ranges indicated, as will be appreciated by those skilled in the art.

Example 13
Insecticide containing cyclic depsipeptide as active ingredient

  Compositions for antimicrobial detergents are prepared by combining the above ingredients in amounts within the ranges indicated, as will be appreciated by those skilled in the art.

Example 14
Non-frozen liquid composition for rapid food freezing For use in agricultural, marine and processed foods.

Example 15
Emulsified light hydrocarbon fuel and method for producing the same

Example 16
Composition for injection molding of inorganic powder and sintered body therefrom

Example 17
Water-soluble coating for walls

* Inorganic hollow beads, talc, wollastonite, and / or pearlite ** Surfactant 1-22, wetting agent 0.1-0.5, rheology agent 0.05-0.5, and cellulose 1-3

Example 18
Towel for skin moisturization and drying

Example 19
Fat and oil compositions comprising natural waxes and edible surfactants for food preservatives or binders

Example 20

Example 21
Lubricant formulation for sheet metal processing

Example 22
Water-based drilling fluid with oil-in-water emulsion

Example 23
Gasoline and diesel fuel

Example 24
Bulky and soft hand-printed paper produced by drying wet paper for paper making containing softener

Example 25
Liquid suspension of polyethylene oxide for flocculation of cellulose fiber suspension and pulp waste liquor

Example 26
Antifoam compositions in the pulp and paper industry

Example 27
Medicine: Vitamin K-containing composition

Example 28
Pharmaceutical composition for transdermal delivery

Example 29
Concentrated antimicrobial agent comprising 1,3-propanediol fatty acid ester for use in food and other applications

Example 30
Non-toxic 1,3-propanediol ester solvent This solvent is suitable for coatings, cosmetics, inks, surfactants, cleaning solvents, adhesives, toiletry products, pharmaceuticals, and agrochemicals.
The alkyd resin was dissolved in a solvent mixture containing 20% 1,3-propanediol monoacetate and 80% 1,3-propanediol diacetate to give a 75% solution.

Example 31
Enteric pharmaceutical composition comprising enzyme-sensitive oily medium Capsule (hard or soft) is made of glycerol fatty acid ester, polyoxysorbitan fatty acid ester, 1,3-propanediol fatty acid ester, ethylene glycol fatty acid ester, and / or decoglycerin fatty acid ester An active ingredient dissolved in a medium containing Thus, even drugs that hardly dissolve can be easily absorbed.

Example 32
Self-adhesive device for transdermal administration of active agents

Example 33
Fatty acid esters of alkanediols as transdermal absorption enhancers

Example 34
Polyolefin fiber hydrophilizing agent for sanitary products

Example 35
Articles coated with antimicrobial compositions comprising fatty acid esters and enhancers

Example 36
Fatty acid esters for use as fungicides with high affinity for fibers and antimicrobial fibers

Example 37
Liquid Powder Surfactant Using the present invention, a liquid powder surfactant can be prepared using a bio-based propanediol caprylate. The components are obtained in proportions listed in Table 1. Starting with the ingredients in Table 1, imulin lauryl carbamate is added to the water and CARBOPOL ULREZ 10 (BF Goodrich Company, New York, NY) is dispersed. Blend the Phase A component mixture for about 10 minutes until the carbomer is fully dispersed and hydrated. Raise the temperature of the mixture to about 70 ° C. under light agitation.

  In a separate clean container, the ingredients listed in Table 1, Phase B, including the bio-based propanediol caprylate, are combined in the amounts specified by the table and heated to about 75 ° C. After the ingredients are fully combined and at the desired temperature, slowly add Phase B mixture to Phase A mixture. Rapid stirring is applied and the temperature is held between about 70 ° C. and about 75 ° C. for 30 minutes. After 30 minutes, the combined mixture is cooled to 55 ° C. and Phase C corn starch is slowly added in the amount specified by the table with continuous stirring. After the corn starch is thoroughly mixed with the combined ingredients of Phases A and B, add Phase C fragrance and preservative. Adjust fragrance and preservative as desired. Measure the pH and adjust the pH between about 5.5 and 6.0 with triethanolamine if necessary. Once the pH is adjusted, cool to room temperature.

Example 38
Glossy Milk Bath The present invention can be used to prepare a glossy milk bath using a bio-based propanediol distearate. According to the percentages in Table 2, UCARE polymer LR-400 is hydrated with a sufficient amount of water. Then blend in PLATOPON 611 L (Fitz Chem Corporation, Itasca, IL) and LAMWSOFT PO 65 (Fitz Chem Corporation, Itasca, IL) according to the percentages listed in the table until the mixture reaches a uniform consistency.

  At this point, the amount of polymer solution listed in the table is added to the mixture and stirred until a uniform consistency is restored. Next, according to the percentages listed in Table X, glycerin, STANDAMOX CAW (Fitz Chem Corporation, Itasca, IL), NUTRILAN MILK (Fitz Chem Corporation, Itasca, IL), bio-based propanediol distearate is added and the mixture Thoroughly mix until a uniform consistency is obtained. The pH is measured and, if necessary, adjusted with citric acid so that the final pH reaches between about 6 and about 7. Finally, preservatives, dyes, fragrances, and enough water are added to reach the desired volume. The final viscosity of the mixture should be between about 5,000 cPs and about 10,000 cPs.

Example 39
Gentle Baby Shampoo The present invention may be used in the preparation of a gentle baby shampoo using a bio-based propanediol oleate. The components in the proportions listed in Table 3 are obtained. Heat slightly less than the amount required according to Table 3 to about 40 ° C. Add ingredients in the amounts and order listed in the table. Mix the ingredients with gentle agitation not exceeding 100 rpm. When the mixture reaches a uniform consistency, water is added to bring the mixture to the desired final volume. Cool the mixture to room temperature. The resulting shampoo is prepared and it must be precisely transparent and colorless.

Example 40
Moisturizing body wash The present application can be used in the preparation of moisturizing body wash with bio-based propanediol stearate. To prepare such a moisturizing body wash, start by obtaining a list of proportional amounts of ingredients listed in the table. Sodium laureth sulfate, JORDAPON CI (BASF Corporation, Mount Olive, NJ), AVANEL S150 CGN (BASF Corporation, Mount Olive, NJ), PEG-150 distearate, cocamidopropyl betaine, cocamide MEA, and biobased propanediol stearate Are mixed together with about half of the total water required for the desired amount. After the ingredients are carefully combined, the mixture is heated to raise the temperature of the mixture to about 65 ° C. A temperature of about 65 ° C. is maintained until all ingredients are dissolved and a uniform mixture is obtained. While the mixture is allowed to cool, LUVIQUAT PQ11 (BASF Corporation, Mount Olive, NJ) is added and stirred gently.

  In a separate container, CREMOPHOR PS20 (BASF Corporation, Mount Olive, NJ), vitamin E acetate, and fragrance are mixed together until completely blended. When the temperature of the first mixture drops below 40 ° C., CREMOPHOR PS20 (BASF Corporation, Mount Olive, NJ), vitamin E acetate, and fragrance are mixed with this mixture. Next, D, L-PANTHENOL 50W (BASF Corporation, Mount Olive, NJ) is added to the mixture and gently stirred until completely blended. Next, D, L-Panthenol 50W is added to the mixture and gently stirred until completely blended. Next, disodium EDTA is added to the mixture and gently stirred until completely blended. Next, a preservative selected to be appropriate with respect to the anticipated conditions and shelf life is added. Finally, water is added to bring the mixture to the desired volume and stirred until a uniform consistency is achieved.

Example 41
Surfactants comprising esters formed from biologically derived 1,3-propanediol

  Addition of fatty acid 1,3-propanediol esters using fatty acid alkanolamides and ether-sulfate-free surfactants results in 1) an excellent gloss effect, 2) good storage capacity, and 3) a gloss dispersion with low viscosity Produce. This composition forms a glossy dispersion with good flow properties and low surfactant content.

Example 42
Liquid surfactants comprising esters formed from biologically derived 1,3-propanediol

  Addition of fatty acid 1,3-propanediol esters using fatty acid alkanolamides and nonionic surfactants 1) excellent pearlescent effect, 2) long shelf life, 3) compatibility with cationic surfactants, This results in a glossy dispersion having 4) resistance to hydrolysis, 5) low viscosity, and 6) reduced foaming.

Example 43
Liquid surfactants comprising esters formed from biologically derived 1,3-propanediol

  In this composition, the fatty acid 1,3-propanediol ester functions as a brightener, the nonionic surfactant functions as an emulsifier and stabilizer, and the amphoteric surfactant as a co-emulsifier to enhance the gloss effect. And glycols function as emulsifiers as well.

Example 44
Liquid surfactants comprising esters formed from biologically derived 1,3-propanediol

  Foaming behavior can be tested by preparing a 10% by weight aqueous surfactant solution (21 ° dH + 1% weight sebum) and determining the foam volume according to standard DIN 53902, part 2. Test solutions can be made using a weight ratio of A (10.0-60.0%) and B (90.0-40.0%). Fatty acid glycol ester sulfate may exhibit the following advantageous properties: 1) foam booster for other surfactants, 2) foam stability in the presence of hard water and / or oil, 3) poor in cold water Improves the surfactant formulation with stability, 4) contributes to cleaning performance, 5) is dermatologically safe, 6) is readily biodegradable, and does not contain nitosamine.

Example 45
Liquid surfactants comprising esters formed from biologically derived 1,3-propanediol

  The composition using 1,3-propanediol ester has a pearly luster and is excellent in the dispersion stability of the gloss.

Procedure-Combine all ingredients, heat to 80 ° C and dissolve components, then cool lysate to 30 ° C with stirring.

Example 46
A bread roll for evaluation of the present invention is prepared according to the following method.

Example 47
A biscuit for evaluation of the present invention is prepared according to the following method.

Example 48
According to the following method ^a , a beverage emulsion stabilizer for evaluation of the present invention is prepared.

^ａｇで与えられた量

^{a The} amount given in g

Example 49

According to the following method ^a , a beaten egg substitute for evaluation of the present invention is prepared.

Example 50
Aerosol composition for animal samples

Example 51
A powder blowing agent for use in cake mixes to improve butter consistency is prepared according to the following procedure.

  Although the invention is described and described herein with reference to specific embodiments, it is not intended that the invention be limited to the details shown. Rather, various modifications may be made in the details within the scope and extent of equivalents of the claims and without departing from the invention.

Comparative Example 1
The properties of poly (lactic acid) (PLA) made using 1,3-propanediol plasticizer and commercially available plasticizer were compared. Specifically, tensile modulus, tensile strength, and elongation at break were measured for each of the PLA blends made using different plasticizers and the blends made without any plasticizer.

  The matrix polymer used was from Cargill, Inc. Poly (butyric acid) (PLA) 4040D from Minnetonka, MN. Esters were synthesized from biologically derived 1,3-propanediol. Ester production, production, and characterization are as described above. The commercial plasticizer ester used was propylene glycol dibenzoate for comparison.

  In forming the polymer, the PLA resin was dried in a vacuum oven at 80 ° C. for 16 hours and then various amounts in a 28 mm twin screw extruder, commercial unit (Werber-Pfleiderer, Ramsey, NJ). Were melt extruded using a plasticizer. The plasticizer was transferred by an infusion pump. Plasticizers that were solid at room temperature melted before use. The PLA pellets and plasticizer blend were dried at 80 ° C. under vacuum prior to the film extrusion process. The dried pellets were extruded through a standard die, quenched by passing through a water cooled roll, cooled to room temperature, and wound. Films of various thicknesses were prepared. The physical properties for the 4 mm film are shown in Table 1 below.

  The physical properties of the extruded film samples are described in Instron Corp. Tensile Tester, Model no. 1125 (Instron Corp., Norwood MA). Tensile properties were measured according to ASTM D-882-02. Each data point is an average of at least 5 individual test samples.

Table 1. Tensile modulus of PLA blends with different plasticizers

Table 2. PLA control and PLA tensile properties using different plasticizers

Table 3. Effect of plasticizer on tensile elongation of PLA blend

  Generally, polyesters containing PLA are not easily plasticized, but plasticizers can act as processing aids. The data in Tables 1 to 3 show that by using an aliphatic ester of 1,3-propanediol (propanediol-di-ethylhexanoate), the elongation at break of PLA is almost 100 compared to a commercially available plasticizer. % Can be increased. The performance of propanediol-dibenzoate is comparable to commercially available ester plasticizers.

Comparative Example 2
The properties of poly (vinyl chloride) (PVC) made using 1,3-propanediol plasticizer and commercially available plasticizer were compared. Specifically, Young's modulus, breaking stress, and breaking strain were measured using each of the PVC blends made with different plasticizers and different weight percentages, and blends made without any plasticizer.

  The 1,3-propanediol ester was synthesized in a manner comparable to that disclosed herein. The 1,3-propanediol ester used is propanediol dibenzoate and the commercial product used is propylene glycol (1,2-propane), available as Benzoflex 284® from Velsicol, Rosemont, IL. Diol) dibenzoate.

  Poly (vinyl chloride) (PVC) Geon (R) 2188GC was obtained from PolyOne, Cleveland, OH. The polymer was mixed with 1,3-propanediol ester and commercially available ester material in an industrial mixer at 60 rpm for 15 minutes. The mixing temperature was maintained between 170-175 ° C. After mixing, the polymer was cooled, ground and dried at 80 ° C. under vacuum under a nitrogen blanket.

  The polymer was press molded with a mold size of 220 nm × 150 nm. Samples are tested for geometric shape ((5) type bar) followed by ASTM D638 requirements. Physical measurements were performed on a test bar (ASTM D638) against Instron Corporation Tensile Tester, Model no. 1125 (Instron, Corp., Newwood MA). The level of plasticizer used and physical test data are incorporated in Table 4.

Table 4. Mechanical properties of plasticized PVC

  Although the invention is described and described herein with reference to specific embodiments, it is not intended to limit the invention to the details shown. Rather, various modifications may be made in the details within the scope and extent of equivalents of the claims and without departing from the invention.

Claims (28)

A composition comprising an ester of 1,3-propanediol, wherein the 1,3-propanediol is biologically derived. The composition of claim 1, wherein the ester has at least 3% biobased carbon. The composition of claim 1, wherein the ester has at least 6% biobased carbon. The composition of claim 1, wherein the ester has at least 10% biobased carbon. The composition of claim 1, wherein the ester has at least 25% biobased carbon. The composition of claim 1, wherein the ester has at least 50% biobased carbon. The composition of claim 1, wherein the ester has at least 75% biobased carbon. The composition of claim 1, wherein the ester has 100% biobased carbon. The ester has the chemical formula R ₁ —C (═O) —O—CH ₂ —CH ₂ —CH ₂ —OH, wherein R ₁ is a linear chain between about 1 and about 40 in length. The composition of claim 1, wherein the composition is a chain or branched carbon chain. R ₁ has one or more functional groups selected from the group consisting of alkenes, amides, amines, carbonyls, carboxylic acids, halides, hydroxyl groups, ethers, alkyl ethers, sulfates, and ether sulfates. Item 10. The composition according to Item 9. The ester has the chemical formula R ₁ —C (═O) —O—CH ₂ —CH ₂ —CH ₂ —O—C (═O) —R ₂ , where R ₁ and R ₂ are about 1 The composition of claim 1, wherein the composition is a linear or branched carbon chain of between about and about 40 carbons in length. R ₁ and R ₂ are one or more functional groups selected from the group consisting of alkenes, amides, amines, carbonyls, carboxylic acids, halides, hydroxyl groups, ethers, alkyl ethers, sulfates, and ether sulfates. The composition of claim 11, wherein: The composition of claim 11, wherein R ₁ and R ₂ are the same carbon chain. The composition of claim 1, wherein the ester is:
i. Propanediol distearate, monostearate, and mixtures thereof;
ii. Propanediol dilaurate, monolaurate, and mixtures thereof;
iii. Propanediol dioleate, monooleate, and mixtures thereof;
iv. Propanediol divalerate, monovalerate, and mixtures thereof;
v. Propanediol dicaprylate, monocaprylate, and mixtures thereof;
vi. Propanediol dimyristate, monomyristate, and mixtures thereof;
vii. Propanediol dipalmitate, monopalmitate, and mixtures thereof;
viii. Propanediol dibehenate, monobehenate, and mixtures thereof;
ix. Propanediol adipate;
x. Propanediol maleate;
xi. Propanediol dibenzoate;
xii. Propanediol diacetate; and xiii. A composition selected from the group consisting of these mixtures. 15. The composition of claim 14, wherein the ester is:
a. Propanediol distearate, monostearate, and mixtures thereof;
b. Propanediol dioleate, monooleate, and mixtures thereof;
c. Propanediol dicaprylate, monocaprylate, and mixtures thereof;
d. Propanediol dimyristate, monomyristate, and mixtures thereof;
e. A composition selected from the group consisting of these mixtures. The composition of claim 1 further comprising a biologically derived 1,3-propanediol. 17. The composition of claim 16, comprising at least 2% biologically derived 1,3-propanediol. 17. The composition of claim 16, comprising at least 5% biologically derived 1,3-propanediol. 17. The composition of claim 16, comprising at least 10% biologically derived 1,3-propanediol. 17. The composition of claim 16, comprising at least 25% biologically derived 1,3-propanediol. 17. The composition of claim 16, comprising at least 50% biologically derived 1,3-propanediol. A process for preparing a composition comprising an ester of 1,3-propanediol, the process comprising:
(A) providing a biologically produced 1,3-propanediol;
(B) contacting 1,3-propanediol with an organic acid, wherein the method comprises producing an ester; and (c) recovering the ester. 23. The method of claim 22, wherein the 1,3-propanediol has at least 95% biobased carbon. 24. The method of claim 22, wherein the 1,3-propanediol has 100% biobased carbon. Biologically produced 1,3-propanediol has the following characteristics: 1) UV absorption of less than about 0.200 at 220 nm and less than about 0.075 at 250 nm and less than about 0.075 at 275 nm; 2 A composition having an L * a * b * “b *” color value of less than about 0.15 and an absorption of less than about 0.075 at 270 nm; 3) a peroxide composition of less than about 10 ppm; and 4) less than about 400 ppm. 23. The method of claim 22, having at least one of: a concentration of total organic impurities. 23. A composition comprising an ester produced in the method of claim 22. A composition comprising an ester of 1,3-propanediol, wherein the ester is a binder, a surfactant, a modifier, a structurant, a foaming agent, a moisturizer, an antifoaming agent, an emulsifier, a fragrance, a gelling agent, Thickeners, stabilizers, surfactants, gelatinizers, texturizers, opacifiers, pearlizing agents, solvents, dispersants, wetting agents, compatibilizers, corrosion inhibitors A composition that functions as a component selected from the group consisting of agents, lubricants, demulsifiers, biocides, and antimicrobial agents. A composition comprising an ester of 1,3-propanediol selected from the group consisting of a personal care composition, a cleaning composition, a plasticizer composition, and a food composition.

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