U.S. patent application number 11/705342 was filed with the patent office on 2007-08-30 for food compositions comprising biologically-based biodegradable 1,3-propanediol esters.
Invention is credited to Gyorgyi Fenyvesi, Melissa Joerger, Robert Miller, Ann Wehner.
Application Number | 20070203323 11/705342 |
Document ID | / |
Family ID | 38372098 |
Filed Date | 2007-08-30 |
United States Patent
Application |
20070203323 |
Kind Code |
A1 |
Fenyvesi; Gyorgyi ; et
al. |
August 30, 2007 |
Food compositions comprising biologically-based biodegradable
1,3-propanediol esters
Abstract
A process for producing a food composition is provided. The food
composition comprises an ester of 1,3-propanediol, and the
1,3-propanediol used to form the ester is biologically-derived. The
process comprises mixing an ester of 1,3-propanediol into a food
composition. Another process includes providing 1,3-propanediol
with at least 90% biobased carbon, contacting the 1,3-propanediol
with an organic acid, which forms the ester, recovering the ester;
and incorporating the ester into a food composition. Also provided
is a composition comprising a 1,3-propanediol ester and a food
ingredient. The food composition can further comprise a glycol
component, and that glycol component can be 1,3-propanediol.
Inventors: |
Fenyvesi; Gyorgyi;
(Wilmington, DE) ; Joerger; Melissa; (Newark,
DE) ; Miller; Robert; (Wilmington, DE) ;
Wehner; Ann; (Hockessin, DE) |
Correspondence
Address: |
MCCARTER & ENGLISH, LLP;BASIL S. KRIKELIS
CITIZENS BANK CENTER, 919 N. MARKET STREET
SUITE 1800
WILMINGTON
DE
19801
US
|
Family ID: |
38372098 |
Appl. No.: |
11/705342 |
Filed: |
February 12, 2007 |
Related U.S. Patent Documents
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Application
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Filing Date |
Patent Number |
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60772471 |
Feb 10, 2006 |
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60772194 |
Feb 10, 2006 |
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60772193 |
Feb 10, 2006 |
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60772111 |
Feb 10, 2006 |
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60772120 |
Feb 10, 2006 |
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60772110 |
Feb 10, 2006 |
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60772112 |
Feb 10, 2006 |
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60846948 |
Sep 25, 2006 |
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60853920 |
Oct 24, 2006 |
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60859264 |
Nov 15, 2006 |
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60872705 |
Dec 4, 2006 |
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60880824 |
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Current U.S.
Class: |
528/272 |
Current CPC
Class: |
A01N 3/00 20130101; C09K
3/185 20130101; C11D 3/38663 20130101; A61K 8/92 20130101; A61K
36/28 20130101; A61K 2800/10 20130101; A61Q 19/002 20130101; C10N
2040/08 20130101; C11D 3/2003 20130101; A61K 31/22 20130101; A23L
3/3463 20130101; A23L 29/10 20160801; A61K 9/282 20130101; C07C
69/28 20130101; C09D 11/03 20130101; C09D 11/16 20130101; C11C
3/003 20130101; A23L 29/035 20160801; A23L 29/04 20160801; C10M
2207/283 20130101; C11D 7/5022 20130101; A61K 36/185 20130101; A61Q
11/00 20130101; A61K 8/0208 20130101; A61Q 1/14 20130101; A61Q 9/02
20130101; A61Q 17/00 20130101; C07C 69/16 20130101; C07C 67/08
20130101; C09K 5/20 20130101; C11D 1/667 20130101; C02F 5/10
20130101; A61K 36/61 20130101; C10M 2207/04 20130101; A61Q 15/00
20130101; C07C 69/78 20130101; C11D 11/0017 20130101; C07C 69/58
20130101; C10M 2207/022 20130101; A23L 33/10 20160801; A61K 47/44
20130101; A61Q 19/00 20130101; C11D 7/266 20130101; C11D 3/2068
20130101; A61K 9/0019 20130101; C07C 69/60 20130101; C09D 7/63
20180101; C12P 7/18 20130101; C12P 7/62 20130101; A61Q 9/04
20130101; C11D 3/2044 20130101; C11D 3/3418 20130101; A61Q 1/08
20130101; A61Q 19/10 20130101; A23K 20/105 20160501; A61K 8/345
20130101; A61Q 1/02 20130101; A61Q 5/065 20130101; A01N 25/02
20130101; A61K 2800/75 20130101; C10M 2209/086 20130101; C10M
2229/0425 20130101; A61K 36/355 20130101; A61K 36/738 20130101;
A23L 2/52 20130101; A61K 36/02 20130101; A61K 47/10 20130101; A61Q
5/00 20130101; A01N 1/021 20130101; A23V 2002/00 20130101; C11D
11/0023 20130101; A61Q 5/02 20130101; A61Q 5/12 20130101; A61Q
19/04 20130101; B01D 11/0288 20130101; A61K 9/06 20130101; A61Q
19/008 20130101; C08K 2201/018 20130101; C07C 69/44 20130101; C09G
1/08 20130101; A61K 47/14 20130101; A61Q 1/10 20130101; A61Q 5/10
20130101; A61Q 19/007 20130101; C09D 11/38 20130101; C09K 3/18
20130101; C10M 2215/223 20130101; C11D 3/2093 20130101; C12P 7/42
20130101; A61K 8/375 20130101; C08K 5/053 20130101; C08K 5/103
20130101; Y02W 10/37 20150501; A61Q 13/00 20130101; C10N 2030/64
20200501; A23L 33/12 20160801; A61Q 19/005 20130101; A21D 2/14
20130101; A61Q 17/005 20130101; C10M 129/08 20130101; C10M 2215/042
20130101; A23B 7/154 20130101; A61Q 17/04 20130101; C09K 5/10
20130101; C08K 5/103 20130101; C08L 67/04 20130101; C07C 67/08
20130101; C07C 69/60 20130101; C07C 67/08 20130101; C07C 69/58
20130101; C07C 67/08 20130101; C07C 69/78 20130101; C07C 67/08
20130101; C07C 69/44 20130101; C07C 67/08 20130101; C07C 69/16
20130101; C07C 67/08 20130101; C07C 69/28 20130101 |
Class at
Publication: |
528/272 |
International
Class: |
C08G 63/02 20060101
C08G063/02 |
Claims
1. A food composition comprising a 1,3-propanediol ester and a food
ingredient.
2. The food composition of claim 1 further comprising a glycol
component.
3. The food composition of claim 1 wherein the glycol component is
1,3-propanediol.
4. The food composition of claim 3 wherein the 1,3-propanediol is
biologically produced through a fermentation process.
5. The food composition of claim 3 wherein the 1,3-propanediol has
at least 90% biobased carbon.
6. The food composition of claim 3 wherein the 1,3-propanediol has
100% biobased carbon.
7. The food composition of claim 4 wherein the 1,3-propanediol has
at least one of the following characteristics: 1) an ultraviolet
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 L*a*b* "b*" color value of less than about 0.15
and an absorbance of 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.
8. The food composition of claim 1 wherein the 1,3-propanediol
ester is at least 3% biobased carbon.
9. The food composition of claim 1 wherein the 1,3-propanediol
ester is at least 6% biobased carbon.
10. The food composition of claim 1 wherein the 1,3-propanediol
ester is at least 10% biobased carbon.
11. The food composition of claim 1 wherein the 1,3-propanediol
ester is at least 25% biobased carbon.
12. The food composition of claim 1 wherein the 1,3-propanediol
ester is at least 50% biobased carbon.
13. The food composition of claim 1 wherein the 1,3-propanediol
ester is 100% biobased carbon.
14. The food composition of claim 1 further comprising water.
15. The food composition of claim 1 wherein the composition is
between about 0.1% to about 50% 1,3 propanediol ester.
16. The food composition of claim 1 wherein the composition is
between about 0.1% to about 15% 1,3 propanediol ester.
17. The food composition of claim 1 wherein the composition is
between about 0.3% to about 5% 1,3 propanediol ester.
18. The food composition of claim 1 wherein the composition is
between about 5% to about 30% 1,3 propanediol ester.
19. The food composition of claim 1 wherein the 1,3 propanediol
ester is an ingredient selected from the group consisting of
binders, foaming agents, emulsifiers, flavoring agents, gelling
agents, thickeners, stabilizers, surface active agents,
gelatinizers, and texturizers.
20. The food composition of claim 1 wherein the ester has the
formula R1-C(.dbd.O)--O--CH2-CH2-CH2-OH, wherein R1 is a linear,
branched, cyclic, or aromatic, and wherein the carbon number is
between about 1 an about 40 carbons.
21. The food composition of claim 1 wherein the ester has the
formula R1-C(.dbd.O)--O--CH2-CH2-CH2-O--C(.dbd.O)--R2, wherein R1
and R2 are linear, branched, cyclic, or aromatic, and wherein the
carbon in R1 and R2 is between about 1 an about 40 carbons
each.
22. The food composition of claim 21 wherein R1 and R2 are the same
carbon chain.
23. The food composition of claim 1, wherein the ester is selected
from one or more members of the group consisting of: i. propanediol
distearate, monostearate and a mixture thereof; ii. propandiol
dilaurate, monolaurate and a mixture thereof; iii. propanediol
dioleate, monooleate and a mixture thereof; iv. propanediol
divalerate, monovalerate and a mixture thereof; v. propanediol
dicaprylate, monocaprylate and a mixture thereof; vi. propanediol
dimyristate, monomyristate and a mixture thereof; vii. propanediol
dipalmitate, monopalmitate and a mixture thereof; viii. propanediol
dibehenate, monobehenate and a mixture thereof; ix. propanediol
adipate; x. propanediol maleate; xi. propanediol monoisostearate;
xii. propanediol dibenzoate; xiii. propanediol diacetate; xiv.
propanediol dilinolate, monolinolate, and a mixture thereof.
24. The food composition of claim 1 wherein the Bio-PDO is selected
from the group consisting of an anticaking agent, free-flow agent,
antioxidant, dough strengthener, emulsifier, emulsifier salt,
flavoring agent, flavoring adjuvant, formulation aid, humectant,
processing aid, solvent, vehicle, stabilizer, thickener,
surface-active agent, and a texturizer.
25. The food composition of claim 1 wherein said food composition
is selected from the group consisting of a human food, a substance
migrating to food from a food-contact article, a beverage, a pet
food, and an animal feed composition.
26. A process for producing a food composition comprising an ester
of 1,3-propanediol, wherein the 1,3-propanediol is
biologically-derived, the process comprising: (a) providing
1,3-propanediol with at least 90% biobased carbon; (b) contacting
the 1,3-propanediol with an organic acid, forming the ester; (c)
recovering the ester; and (d) incorporating the ester into a food
composition.
27. The process of claim 26 wherein the organic acid has the
formula R--COOH, wherein the substituent R can be a saturated or
unsaturated, substituted or unsubstituted, linear or branched,
cyclic or aromatic hydrocarbon having carbon numbers 1 to 40, or
its salts or its alkyl esters.
28. The process of claim 26, wherein the organic acid has the
formula R--COOH, and the substituent R can have one or more
functional groups such as alkene, amide, amine, carbonyl,
carboxylic acid, halide, hydroxyl groups, ether, alkyl ether,
sulfate and ethersulfate.
29. The process of claim 26 wherein the organic acid is a naturally
derived organic acid.
30. The process of claim 26 wherein the organic acid is selected
from the group consisting of: acetic, butyric, lauric, myristic,
palmitic, stearic, arachidic, adipic, benzoic, caprylic, maleic,
palmitic, sebacic, archidonic, erucic, palmitoleic, pentadecanoic,
heptadecanoic, nondecanoic, octadectetraenoic, eicosatetraenoic,
eicosapentaenoic, docasapentaenoic, tetracosapentaenoic,
tetrahexaenoic, docosahexenoic, (alpha)-linolenic, docosahexaenoic,
eicosapentaenoic, linoleic, arachidonic, oleic, erucic, formic,
propionic, valeric, caproic, capric, malonic, succinic, glutaric,
adipic, pimelic, suberic, azelaic, tartaric, citric, salicylic,
acetyl-salicylic, pelargonic, behenic, cerotic, margaric, montanic,
melissic, lacceroic, ceromelissic, geddic; ceroplastic,
undecylenic, ricinoleic, elaeostearic acid, and mixtures thereof.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims the benefit of U.S.
Provisional Application Ser. No. 60/772,471, filed Feb. 10, 2006;
U.S. Provisional Application No. 60/772,194, filed Feb. 10, 2006,
U.S. Provisional Application No. 60/772,193, filed Feb. 10, 2006,
U.S. Provisional Application No. 60/772,111, filed Feb. 10, 2006,
U.S. Provisional Application No. 60/772,120, filed Feb. 10, 2006,
U.S. Provisional Application No. 60/772,110, filed Feb. 10, 2006,
U.S. Provisional Application No. 60/772,112, filed Feb. 10, 2006,
U.S. Provisional Application No. 60/846,948, filed Sep. 25, 2006,
U.S. Provisional Application No. 60/853,920, filed Oct. 24, 2006,
U.S. Provisional Application No. 60/859,264, filed Nov. 15, 2006,
U.S. Provisional Application No. 60/872,705, filed Dec. 4, 2006 and
U.S. Provisional Application No. 60/880,824, filed Jan. 17, 2007,
the disclosures of which are expressly incorporated herein by
reference in their entireties.
FIELD OF THE INVENTION
[0002] The field of the invention relates generally to food
compositions, and more specifically to food compositions comprising
esters of 1,3-propanediol.
BACKGROUND OF THE INVENTION
[0003] Esters produced from glycols such as ethylene glycol,
propylene glycol, 1,3-butylene glycol, and 2-methyl-1,3-propanediol
are compounds that are useful in food and beverage compositions, as
well as in animal feed compositions. Glycol esters are used in
food, feed, and beverage products as emulsifiers, thickeners,
stabilizers, and gelatinizers.
[0004] Consumers and manufacturers are increasingly concerned with
the environmental impact of all products. The effort towards
environmental impact awareness is a universal concern, recognized
by government agencies. The Kyoto Protocol amendment to the United
Nations Framework Convention on Climate Change (UNFCCC) currently
signed by 156 nations is one example of a global effort to favor
safer environmental manufacturing over cost and efficiency.
Consumers are increasingly selective about the origins of the
products they purchase. The 2004 Co-operative Bank's annual Ethical
Consumerism Report (www.co-operativebank.co.uk) disclosed a 30.3%
increase in consumer spending on ethical retail products (a general
classification for environmental safe, organic and fair trade
goods) between 2003 and 2004 while total consumer spending during
the same period rose only 3.7%.
[0005] One of the single greatest environmental concerns to
consumers is the global warming effect and greenhouse gases that
contribute to the effect. Greenhouse gases are gases that allow
sunlight to enter the atmosphere freely. When sunlight strikes the
Earth's surface, some of it is reflected back towards space as
infrared radiation. Greenhouse gases absorb this infrared radiation
and trap the heat in the atmosphere. Over time, the amount of
energy sent from the sun to the Earth's surface should be about the
same as the amount of energy radiated back into space, leaving the
temperature of the Earth's surface roughly constant. However,
increasing the quantity of greenhouse gases above the quantity that
existed before the rise of human industrialization is thought to
increase the retained heat on the Earth's surface and produce the
global warming observed in the last two centuries.
[0006] Carbon dioxide is singled out as the largest component of
the collection of greenhouse gases in the atmosphere. The level of
atmospheric carbon dioxide has increased 50% in the last two
hundred years. Any further addition of carbon dioxide to the
atmosphere is thought to further shift the effect of greenhouse
gases from stabilization of global temperatures to that of heating.
Consumers and environmental protection groups alike have identified
industrial release of carbon into the atmosphere as the source of
carbon causing the greenhouse effect. Only organic products
composed of carbon molecules from renewably based sources such as
plant sugars and starches and ultimately atmospheric carbon are
considered to not further contribute to the greenhouse effect, when
compared to the same organic molecules that are petroleum or fossil
fuel based.
[0007] In addition to adding carbon dioxide to the atmosphere,
current methods of industrial production of propanediols produce
contaminants and waste products that include among them sulfuric
acid, hydrochloric acid, hydrofluoric acid, phosphoric acid,
tartaric acid, acetic acids, alkali metals, alkaline earth metals,
transitional metals and heavy metals, including Iron, cobalt,
nickel, copper, silver, molybdenum, tungsten, vanadium, chromium,
rhodium, palladium, osmium, iridium, rubidium, and platinum (U.S.
Pat. Nos. 2,434,110, 5,034,134, 5,334,778, and 5,10,036).
[0008] There is a need for all manufactures to provide products
reduced environmental impacts, and to especially consider the
carbon load on the atmosphere. There is also an environmental
advantage for manufacturers to provide products of renewably based
sources.
[0009] Published U.S. Patent Application No. 2005/0069997 discloses
a process for purifying 1,3-propanediol from the fermentation broth
of a cultured E. coli that has been bioengineered to synthesize
1,3-propanediol from sugar. The basic process entails filtration,
ion exchange and distillation of the fermentation broth product
stream, preferably including chemical reduction of the product
during the distillation procedure. Also provided are highly
purified compositions of 1,3-propanediol
SUMMARY OF THE INVENTION
[0010] A process for producing a food composition is provided. The
food composition comprises an ester of 1,3-propanediol, and the
1,3-propanediol used to form the ester is biologically-derived. The
process comprises mixing an ester of 1,3-propanediol into a food
composition. Another process includes providing 1,3-propanediol
with at least 90% biobased carbon, contacting the 1,3-propanediol
with an organic acid, which forms the ester, recovering the ester;
and incorporating the ester into a food composition. Also provided
is a composition comprising a 1,3-propanediol ester and a food
ingredient. The food composition can further comprise a glycol
component, and that glycol component can be 1,3-propanediol.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is diagram of nuclear magnetic resonance spectra of
the products obtained in Example 3. The figure plots the following
values: (CDCl.sub.3): .delta.=0.88 (t, CH3-CH2, 6H), 1.26 (t,
CH2-CH2-CH2, 28H), 1.61 (t, CH2-CH2-C.dbd.O, 4H), 1.97 (t,
--O--CH2-CH2-CH2-O, 2H), 2.28 (t, CH2-C.dbd.O, 4H), 4.15 (t,
C(.dbd.O)--O--CH2-4H).
[0012] FIG. 2 is a DSC (Differential Scanning Calorimetry) curve of
the product obtained in Example 3. DSC (Tm=66.4.degree. C. and
Tc=54.7.degree. C.).
[0013] FIG. 3 is diagram of nuclear magnetic resonance spectra of
the products obtained in example 4. The figure plots the following
values: .delta.=0.88 (t, CH3-CH2, 6H), 1.26 (t, CH2-CH2-CH2, 28H),
1.61 (t, CH2-CH2-C.dbd.O, 4H), 1.97 (t, --O--CH2-CH2-CH2-O, 2H),
2.28 (t, CH2-C.dbd.O, 4H), 4.15 (t, C(.dbd.O)--O--CH2-4H).
[0014] FIG. 4 is diagram of nuclear magnetic resonance spectra of
the recrystallized products obtained in example 5. The figure plots
the following values: .delta.=0.88 (t, CH3-CH2), 1.27 (t,
CH2-CH2-CH2), 1.60 (t, CH2-CH2-C.dbd.O), 1.87 and 1.96 (t,
--O--CH2-CH2-CH2-O), 2.31 (t, CH2-C.dbd.O), 3.70 (t, HO--CH2-CH2-),
4.15 and 4.24 (t, C(.dbd.O)--O--CH2-).
[0015] FIG. 5 is diagram of nuclear magnetic resonance spectra of
the products obtained in example 6. The figure plots the following
values: .delta.=0.88 (t, CH3-CH2), 1.27 (t, CH2-CH2-CH2), 1.63 (t,
CH2-CH2-C.dbd.O), 1.82, 1.87 and 1.96 (t, --O--CH2-CH2-CH2-O), 2.31
(t, CH2-C.dbd.O), 3.69 and 3.86 (t, HO--CH2-CH2-), 4.15 and 4.21
(t, C(.dbd.O)--O--CH2-).
[0016] FIG. 6 is diagram of nuclear magnetic resonance spectra of
the products obtained in example 7. The figure plots the following
values: .delta.=0.88 (t, CH3-CH2), 1.27 (t, CH2-CH2-CH2), 1.60 (t,
CH2-CH2-C.dbd.O), 1.87 and 1.96 (t, --O--CH2-CH2-CH2-O), 2.31 (t,
CH2-C.dbd.O), 3.70 (t, HO--CH2-CH2-), 4.15 and 4.24 (t,
C(.dbd.O)--O--CH2-).
[0017] FIG. 7 is diagram of nuclear magnetic resonance spectra of
the products obtained in example 8. The figure plots the following
values: .delta.=0.88 (t, CH3-CH2), 1.27 (t, CH2-CH2-CH2), 1.63 (t,
CH2-CH2-C.dbd.O), 1.82, 1.87 and 1.96 (t, --O--CH2-CH2-CH2-O), 2.31
(t, CH2-C.dbd.O), 3.70 and 3.86 (t, HO--CH2-CH2-), 4.15 and 4.24
(t, C(.dbd.O)--O--CH2-).
BIOLOGICAL DEPOSITS
[0018] The transformed E. coli DH5a containing cosmid pKP1
containing a portion of the Klebsiella genome encoding the glycerol
dehydratase enzyme was deposited on 18 Apr. 1995 with the ATCC
under the terms of the Budapest Treaty and is identified by the
ATCC number ATCC 69789. The transformed E. coli DH5a containing
cosmid pKP4 containing a portion of the Klebsiella genome encoding
a diol dehydratase enzyme was deposited on 18 Apr. 1995 with the
ATCC under the terms of the Budapest Treaty and is identified by
the ATCC number ATCC 69790. As used herein, "ATCC" refers to the
American Type Culture Collection international depository located
at 10801 University Boulevard, Manassas, Va., 20110 2209, U.S.A.
The "ATCC No." is the accession number to cultures on deposit with
the ATCC.
DETAILED DESCRIPTION OF THE INVENTION
[0019] Applicants specifically incorporate the entire content of
all cited references in this disclosure. Further, when an amount,
concentration, or other value or parameter is given as either a
range, preferred range, or a list of upper preferable values and
lower preferable values, this is to be understood as specifically
disclosing all ranges formed from any pair of any upper range limit
or preferred value and any lower range limit or preferred value,
regardless of whether ranges are separately disclosed. Where a
range of numerical values is recited herein, unless otherwise
stated, the range is intended to include the endpoints thereof, 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.
[0020] Food compositions comprising esters formed from
biologically-based 1,3-propanediol are presented. The conjugate
esters of biologically-based 1,3-propanediol can be used as food
ingredients, food additives, feed, feed additives, beverage
components, beverages, and related compositions. Also provided are
food compositions containing both biologically-derived
1,3-propanediol and esters of 1,3-propanediol.
[0021] The 1,3 propanediol esters can be used as useful ingredients
for the purpose of functioning as binders, foaming agents,
emulsifers, flavoring agents, gelling agents, thickeners,
stabilizers, surface active agents, gelatinizers, and texturizers,
depending on the food composition.
[0022] Fatty acid monoesters and diesters of biologically-produced
1,3 propanediol are formed by esterification of biologically
derived 1,3-propanediol. Biologically-derived 1,3-propanediol can
be obtained through catalytic conversion of non-fossil fuel carbon
via fermentation with an organism that is able to synthesize
1,3-propanediol. The process provides 1,3-propanediol and its
conjugate monoesters and diesters without introducing additional
carbon into the atmosphere during the production, use, or disposal
of the material.
[0023] Biologically produced 1,3 propanediol represents a new
feedstock for useful monoesters and diesters of 1,3 propanediol.
Such monoesters and diesters have not previously been produced from
a biosourced monomer. As such, new compositions of matter,
comprising 1,3 propanediol esters derived from biosourced carbon
substrates are provided. These compositions may be distinguished
from similar compositions derived from all petrochemical carbon on
the basis of biobased carbon content.
[0024] The terms used in this application shall be accorded the
following definitions:
[0025] The terms "bio-PDO esters", "bio-based PDO ester",
"biologically-derived-PDO esters" and "biologically-based
1,3-propanediol esters" and similar terms as used herein refer to
monoesters and diesters produced from biologically produced
1,3-propanediol.
[0026] The terms "bioPDO", "bio-produced PDO",
"biologically-produced 1,3-propanediol", "bio-derived
1,3-propanediol" and "biologically derived 1,3-propanediol" and
similar terms as used here in refer to 1,3-propanediol derived from
microorganism metabolism of plant-derived sugars composed of carbon
of atmospheric origin, and not composed of fossil-fuel carbon.
[0027] "Substantially purified," as used by applicants to describe
the biologically-produced 1,3-propanediol produced by the process
of the invention, denotes a composition comprising 1,3-propanediol
having at least one of the following characteristics: 1) an
ultraviolet absorption at 220 nm of less than about 0.200 and at
250 nm of less than about 0.075 and at 275 nm of less than about
0.075; or 2) a composition having L*a*b* "b*" color value of less
than about 0.15 and an absorbance at 270 nm of less than about
0.075; or 3) a peroxide composition of less than about 10 ppm; or
4) a concentration of total organic impurities of less than about
400 ppm.
[0028] A "b*" value is the spectrophotometrically determined
"Yellow Blue measurement as defined by the CIE L*a*b* measurement
ASTM D6290.
[0029] The abbreviation "AMS" refers to accelerator mass
spectrometry.
[0030] "Biologically produced" means organic compounds produced by
one or more species or strains of living organisms, including
particularly strains of bacteria, yeast, fungus and other microbes.
"Bio-produced" and biologically produced are used synonymously
herein. Such organic compounds are composed of carbon from
atmospheric carbon dioxide converted to sugars and starches by
green plants.
[0031] "Biologically-based" means that the organic compound is
synthesized from biologically produced organic components. It is
further contemplated that the synthesis process disclosed herein is
capable of effectively synthesizing other monoesters and diesters
from bio-produced alcohols other than 1,3-propanediol; particularly
including ethylene glycol, diethylene glycol, triethylene glycol,
-, dipropylene diol, tripropylene diol, 2-methyl 1,3-propanediol,
neopentyl glycol and bisphenol A. "Bio-based", and "bio-sourced";
"biologically derived"; and "bio-derived" are used synonymously
herein.
[0032] "Fermentation" as used refers to the process of metabolizing
simple sugars into other organic compounds. As used herein
fermentation specifically refers to the metabolism of plant derived
sugars, such sugar are composed of carbon of atmospheric
origin.
[0033] "Carbon of atmospheric origin" as used herein refers to
carbon atoms from carbon dioxide molecules that have recently, in
the last few decades, been free in the earth's atmosphere. Such
carbons in mass are identifiable by the present of particular
radioisotopes as described herein. "Green carbon", "atmospheric
carbon", "environmentally friendly carbon", "life-cycle carbon",
"non-fossil fuel based carbon", "non-petroleum based carbon",
"carbon of atmospheric origin", and "biobased carbon" are used
synonymously herein.
[0034] "Carbon of fossil origin" as used herein refers to carbon of
petrochemical origin. Such carbon has not been exposed to UV rays
as atmospheric carbon has, therefore masses of carbon of fossil
origin has few radioisotopes in their population. Carbon of fossil
origin is identifiable by means described herein. "Fossil fuel
carbon", "fossil carbon", "polluting carbon", "petrochemical
carbon", "petro-carbon" and carbon of fossil origin are used
synonymously herein.
[0035] "Naturally occurring" as used herein refers to substances
that are derived from a renewable source and/or are produced by a
biologically-based process.
[0036] "Fatty acid" as used herein refers to carboxylic acids that
are often have long aliphatic tails, however, carboxylic acids of
carbon length 4-40 are specifically included in this definition for
the purpose of describing the present invention. "Fatty acid
esters" as used herein are esters, which are composed of such,
defined fatty acids.
[0037] "Catalyst" as used herein refers to a substance that is
facilitates a chemical reaction without being either a reactant or
a product of said reaction.
[0038] By the acronym "NMR" is meant nuclear magnetic
resonance.
[0039] By the terms "color" and "color bodies" is meant the
existence of visible color that can be quantified using a
spectrocolorimeter in the range of visible light, using wavelengths
of approximately 400-800 nm, and by comparison with pure water.
Reaction conditions can have an important effect on the nature of
color production. Examples of relevant conditions include the
temperatures used, the catalyst and amount of catalyst. While not
wishing to be bound by theory, we believe color precursors include
trace amounts of impurities comprising olefinic bonds, acetals and
other carbonyl compounds, peroxides, etc. At least some of these
impurities may be detected by such methods as UV spectroscopy, or
peroxide titration.
[0040] "Color index" refers to an analytic measure of the
electromagnetic radiation-absorbing properties of a substance or
compound.
[0041] "Hydrogenation reactor" refers to any of the known chemical
reactors known in the literature, including but not limited to
shaker-tubes, batch autoclaves, slurry reactors, up-flow packed
bed, and trickle flow packed bed reactors.
[0042] The abbreviation "IRMS" refers to measurements of CO2 by
high precision stable isotope ratio mass spectrometry.
[0043] The term "carbon substrate" means any carbon source capable
of being metabolized by a microorganism wherein the substrate
contains at least one carbon atom.
[0044] Unless otherwise stated, all percentages, parts, ratios,
etc., are by weight. Trademarks are shown in upper case. Further,
when an amount, concentration, or other value or parameter is given
as either a range, preferred range or a list of upper preferable
values and lower preferable values, this is to be understood as
specifically disclosing all ranges formed from any pair of any
upper range limit or preferred value and any lower range limit or
preferred value, regardless of whether ranges are separately
disclosed.
[0045] A small amount of the carbon dioxide in the atmosphere is
radioactive. This 14C carbon dioxide is created when nitrogen is
struck by an ultra-violet light produced neutron, causing the
nitrogen to lose a proton and form carbon of molecular weight 14
which is immediately oxidized in carbon dioxide. This radioactive
isotope represents a small but measurable fraction of atmospheric
carbon. Atmospheric carbon dioxide is cycled by green plants to
make organic molecules during the process known as photosynthesis.
The cycle is completed when the green plants or other forms of life
metabolize the organic molecules producing carbon dioxide which is
released back to the atmosphere. Virtually all forms of life on
Earth depend on this green plant production of organic molecule to
produce the chemical energy that facilitates growth and
reproduction. Therefore, the 14C that exists in the atmosphere
becomes part of all life forms, and their biological products.
These renewably based organic molecules that biodegrade to CO2 do
not contribute to global warming as there is no net increase of
carbon emitted to the atmosphere. In contrast, fossil fuel based
carbon does not have the signature radiocarbon ratio of atmospheric
carbon dioxide.
[0046] Assessment of the renewably based carbon in a material can
be performed through standard test methods. Using radiocarbon and
isotope ratio mass spectrometry analysis, the biobased content of
materials can be determined. ASTM International, formally known as
the American Society for Testing and Materials, has established a
standard method for assessing the biobased content of materials.
The ASTM method is designated ASTM-D6866.
[0047] The application of ASTM-D6866 to derive a "biobased content"
is built on the same concepts as radiocarbon dating, but without
use of the age equations. The analysis is performed by deriving a
ratio of the amount of radiocarbon (.sup.14C) in an unknown sample
to that of a modern reference standard. The ratio is reported as a
percentage with the units "pMC" (percent modern carbon). If the
material being analyzed is a mixture of present day radiocarbon and
fossil carbon (containing no radiocarbon), then the pMC value
obtained correlates directly to the amount of Biomass material
present in the sample.
[0048] The modern reference standard used in radiocarbon dating is
a NIST (National Institute of Standards and Technology) standard
with a known radiocarbon content equivalent approximately to the
year AD 1950. AD 1950 was chosen since it represented a time prior
to thermo-nuclear weapons testing which introduced large amounts of
excess radiocarbon into the atmosphere with each explosion (termed
"bomb carbon"). The AD 1950 reference represents 100 pMC.
[0049] "Bomb carbon" in the atmosphere reached almost twice normal
levels in 1963 at the peak of testing and prior to the treaty
halting the testing. Its distribution within the atmosphere has
been approximated since its appearance, showing values that are
greater than 100 pMC for plants and animals living since AD 1950.
It's gradually decreased over time with today's value being near
107.5 pMC. This means that a fresh biomass material such as corn
could give a radiocarbon signature near 107.5 pMC.
[0050] Combining fossil carbon with present day carbon into a
material will result in a dilution of the present day pMC content.
By presuming 107.5 pMC represents present day biomass materials and
0 pMC represents petroleum derivatives, the measured pMC value for
that material will reflect the proportions of the two component
types. A material derived 100% from present day soybeans would give
a radiocarbon signature near 107.5 pMC. If that material was
diluted with 50% petroleum derivatives, it would give a radiocarbon
signature near 54 pMC.
[0051] A biomass content result is derived by assigning 100% equal
to 107.5 pMC and 0% equal to 0 pMC. In this regard, a sample
measuring 99 pMC will give an equivalent biobased content result of
93%.
[0052] Assessment of the materials described herein were done in
accordance with ASTM-D6866. The mean values quoted in this report
encompasses an absolute range of 6% (plus and minus 3% on either
side of the biobased content value) to account for variations in
end-component radiocarbon signatures. It is presumed that all
materials are present day or fossil in origin and that the desired
result is the amount of biobased component "present" in the
material, not the amount of biobased material "used" in the
manufacturing process.
[0053] Compositions in accordance with the invention include a
composition comprising an ester of 1,3-propanediol. The esters can
have a varying amount of biobased carbon depending on the compound
used in the esterification. Biologically derived 1,3-propanediol
contains biobased carbon. All three carbon atoms in 1,3 propanediol
are biobased carbons. If the conjugate esters are formed using
carboxylic acids that contain all biobased carbon, then the
resulting esters also contain all biobased carbon. If, however, the
carboxylic acids contain non-biobased carbons, i.e. carbons from a
fossil fuel source, then the resulting ester will contain a
percentage of biobased carbon in proportion to the number of
carbons contributed from the carboxylic acid compared to the three
carbons contributed from the biologically-derived
1,3-propanediol.
[0054] For example, distearate propanediol contains 39 carbon
atoms, 18 from each of the stearic acid carbon chains and three
from the 1,3-propanediol. Accordingly, if the strearic acid is
non-biobased, 36 carbons out of the total 39 in distearate
propanediol are non-biobased carbon. The predicted theoretical
biobased content of distearate propanediol made from
biologically-derived propanediol, and non-biologically derived
strearic acid is approximately 7.7 percent.
[0055] In an analysis performed using the ASTM-D6866 method,
propylene glycol dibenzoate (BENZOFLEX.RTM. 284, Velsicol Chem.
Corp. Rosemont, Ill.) was found to have 0% bio-based carbon
content. The same analysis of propanediol dibenzoate, synthesized
using biologically-derived 1,3-propanediol had 19% bio-based carbon
content. The predicted bio-based carbon content propanediol
dibenzoate made from biologically-derived 1,3 propanediol is 17.6%,
which is within the standard deviation of the method.
[0056] If the stearic acid in the above example is biobased, the
resulting distearate propanediol would have a biobased content of
100%. Accordingly, the conjugate esters of biologically-derived
1,3-propanediol have biobased content values proportional to the
biobased content of the acids used to form the esters. The esters
therefore can have biobased content of 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%
biobased carbon, and 100% biobased carbon.
[0057] If the organic acid is steric acid or oleic acid, the ester
recovered should be greater than 5% biobased carbon. When the
organic acid is lauric acid, the ester recovered should be greater
than 10% biobased carbon.
[0058] Biologically-Derived 1,3-propanediol
[0059] Biologically-derived 1,3-propanediol is collected in a high
purity form. Such 1,3-propanediol has at least one of the following
characteristics: 1) an ultraviolet absorption at 220 nm of less
than about 0.200 and at 250 nm of less than about 0.075 and at 275
nm of less than about 0.075; or 2) a composition having L*a*b* "b*"
color value of less than about 0.15 and an absorbance at 270 nm of
less than about 0.075; or 3) a peroxide composition of less than
about 10 ppm; or 4) a concentration of total organic impurities of
less than about 400 ppm. A "b*" value is the spectrophotometrically
determined Yellow Blue measurement as defined by the CIE L*a*b*
measurement ASTM D6290.
[0060] The level of 1,3-propanediol purity can be characterized in
a number of different ways. For example, measuring the remaining
levels of contaminating organic impurities is one useful measure.
Biologically-derived 1,3-propanediol can have a purity level of
less than about 400 ppm total organic contaminants; preferably less
than 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.
[0061] Biologically-derived 1,3-propanediol can also be
characterized using a number of other parameters, such as
ultraviolet light absorbance at varying wavelengths. The
wavelengths 220 nm, 240 nm and 270 nm have been found to be useful
in determining purity levels of the composition.
Biologically-derived 1,3-propanediol can have a purity level
wherein the UV absorption at 220 nm is less than about 0.200 and at
240 nm is less than about 0.075 and at 270 nm is less than about
0.075.
[0062] Biologically-derived 1,3-propanediol can have a b* color
value (CIE L*a*b*) of less than about 0.15.
[0063] The purity of biologically-derived 1,3-propanediol
compositions can also be assessed in a meaningful way by measuring
levels of peroxide. Biologically-derived 1,3-propanediol can have a
concentration of peroxide of less than about 10 ppm.
[0064] It is believed that the aforementioned purity level
parameters for biologically-derived and purified 1,3-propanediol
(using methods similar or comparable to those disclosed in U.S.
Patent Application No. 2005/0069997) distinguishes such
compositions from 1,3-propanediol compositions prepared from
chemically purified 1,3-propanediol derived from petroleum
sources.
[0065] 1,3-propanediol produced biologically via fermentation is
known, including in U.S. Pat. No. 5,686,276, U.S. Pat. No.
6,358,716, and U.S. Pat. No. 6,136,576, which disclose a process
using a recombinantly-engineered bacteria that is able to
synthesize 1,3-propanediol during fermentation using inexpensive
green carbon sources such as glucose or other sugars from plants.
These patents are specifically incorporated herein by reference.
Biologically-derived 1,3-propanediol can be obtained based upon use
of the fermentation broth generated by a genetically-engineered
Eschericia coli (E. coli), as disclosed in U.S. Pat. No. 5,686,276.
Other single organisms, or combinations of organisms, may also be
used to biologically produce 1,3-propanediol, using organisms that
have been genetically-engineered according to methods known in the
art. "Fermentation" refers to a system that catalyzes a reaction
between substrate(s) and other nutrients to product(s) through use
of a biocatalyst. The biocatalysts 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 in,
for example, Published U.S. Patent Application No. 2005/0069997
incorporated herein by reference.
[0066] Biologically derived 1,3-propanediol contains carbon from
the atmosphere incorporated by plants, which compose the feedstock
for the production of biologically derived 1,3-propanediol. In this
way, the biologically derived 1,3-propanediol contains only
renewable carbon, and not fossil fuel based, or petroleum based
carbon. Therefore the use of biologically derived 1,3-propanediol
and its conjugate esters has less impact on the environment as the
1,3-propanediol does not deplete diminishing fossil fuels. The use
of biologically derived 1,3-propanediol and its conjugate esters
also does not make a net addition of carbon dioxide to the
atmosphere, and thus does not contribute to greenhouse gas
emissions. Accordingly, the present invention can be characterized
as more natural and having less environmental impact than similar
compositions comprising petroleum based glycols.
[0067] Moreover, as the purity of the biologically derived
1,3-propanediol utilized in the food compositions described herein
is higher than chemically synthesized pdo and other glycols, risk
of introducing impurities that may be unacceptable in food
applications is reduced by its use over commonly used glycols, such
as propylene glycol.
[0068] In one embodiment of the invention, a composition comprising
1,3-propanediol and an ester of 1,3-propanediol is provided, where
the 1,3-propanediol is biologically derived. The
biologically-derived 1,3-propanediol in these compositions can have
at least 85% biobased carbon, at least 95% biobased carbon, or 100%
biobased carbon, when assessed by the application of ASTM-D6866 as
described above.
[0069] A sample of biologically-derived 1,3-propanediol was
analyzed using ASTM method D 6866-05. The results received from
Iowa State University demonstrated that the above sample was 100%
bio-based content. In a separate analysis, also performed using a
ASTM-D6866 method, chemical, or petroleum-based 1,3-propanediol
(purchased from SHELL) was found to have 0% bio-based content.
Propylene glycol (USP grade from ALDRICH) was found to have 0%
bio-based content.
[0070] It is contemplated herein that other renewably-based or
biologically-derived glycols, such as ethylene glycol or 1,2
propylene glycol, diethylene glycol, triethylene glycol among
others, can be used in the food compositions of the present
invention.
[0071] There may be certain instances wherein food compositions of
the invention may comprise a combination of a biologically-derived
1,3-propanediol and one or more non biologically-derived glycol
components, such as, for example, chemically synthesized
1,3-propanediol. In such occasions, it may be difficult, if not
impossible to determine which percentage of the glycol composition
is biologically-derived, other than by calculating the bio-based
carbon content of the glycol component. In this regard, in the food
compositions of the invention, the 1,3-propanediol use to form 1,3
propanediol esters, can comprise at least about 1% bio-based carbon
content up to 100% bio-based carbon content, and any percentage
there between.
Ester Conjugates of Biologically Derived 1,3-Propanediol
[0072] Esters of biologically derived 1,3-propanediol, "bio-PDO"
can be synthesized by contacting bio-PDO with an organic acid. The
organic acid can be from any origin, preferably either a biosource
or synthesized from a fossil source. Most preferably the organic
acid is derived from natural sources or bio-derived having formula
R1-COOH. Where in the substituent R1 can be saturated or
unsaturated, substituted or unsubstituted, aliphatic or aromatic,
linear or branched hydrocarbon having chain length 1 to 40 or their
salts or alkyl esters. The hydrocarbon chain can also have one or
more functional groups such as alkene, amide, amine, carbonyl,
carboxylic acid, halide, hydroxyl groups. Naturally occurring
organic acids produced esters containing all biobased carbon. These
naturally occurring organic acids, especially those produced by a
biological organism, are classified as bio-produced and the
resulting ester or diester could thereby also be classified as
bio-produced. Naturally occurring 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, rape seed oil. Conventional fractionation and/or
hydrolysis techniques can be used if necessary to obtain the fatty
acids from such materials.
[0073] Appropriate carboxylic acids for producing esters of
biologically-derived 1,3-propanediol generally include: (1) C1-C3
carbon containing mono carboxylic acids, including formic acid and
acetic acid; (2) fatty acids, such as those acids containing four
or more carbon atoms; (3) saturated fatty acids, such as butyric
acid, caproic acid, valeric acid, caprylic acid, capric acid,
lauric acid, myristic acid, palmitic acid, stearic acid, arachidic
acid, and behenic acid; (4) unsaturated fatty acids, such as oleic
acid, linoleic acid, and euricic acid; (5) polyunsaturated fatty
acids, such as alpha-linolenic acid, stearidonic acid (or moroctic
acid), eicosatetraenoic acid, omega-6 fatty acids, arachidonic
acids, and omege-3 fatty acids, eicosapentaenoic acid (or
timnodonic acid), dosocapentaenoic acid (or clupanodonic acid), and
docosahexaenoic acid (or cervonic acid); (6) hydroxy fatty acids,
such as 2-hydroxy linoleic acid, and recinoleic acid;
phenylalkanoic fatty acids, such as 11-phenyl undecanoic acid,
13-phenyl tridecanoid acid, and 15-phenyl tridecanoid acid; and (7)
cyclohexyl fatty acids, such as 11-cyclohexyl undecanoic acid, and
13-cyclohexyl tridecanoic acid.
[0074] The following acids and their salts or alkyl esters are
specifically useful, acetic, alginic, butyric, lauric, myristic,
palmitic, stearic, arachidic, adipic, benzoic, caprylic, maleic,
palmitic, sebacic, archidonic, erucic, palmitoleic, pentadecanoic,
heptadecanoic, nondecanoic, octadectetraenoic, eicosatetraenoic,
eicosapentaenoic, docasapentaenoic, tetracosapentaenoic,
tetrahexaenoic, docosahexenoic, (alpha)-linolenic, docosahexaenoic,
eicosapentaenoic, linoleic, arachidonic, oleic, erucic, formic,
propionic, valeric, caproic, capric, malonic, succinic, glutaric,
adipic, pimelic, suberic, azelaic, tartaric, citric, salicylic,
acetyl-salicylic, pelargonic, behenic, cerotic, margaric, montanic,
melissic, lacceroic, ceromelissic, geddic, ceroplastic undecylenic,
ricinoleic, and elaeostearic acid as well as mixtures of such
acids. A more preferred list of suitable organic acids are acetic,
adipic, benzoic, maleic, sebacic, and mixtures of such acids. A
more preferred list of suitable "fatty acids" meaning generally
acids named containing 8-40 carbon in the carbon useful in the
present invention include butyric, valeric, caproic, caprylic,
pelargonic, capric, lauric, myristic, palmitic, stearic, arachidic,
behenic, cerotic, oleic, linoleic, linolenic, margaric, montanic,
melissic, lacceroic, ceromelissic, geddic, ceroplastic and the
mixtures of such acids. Among those acids, these acids, and their
salts and alkyl esters are most preferred stearic, lauric,
palmetic, oleic, 2-ethyl hexanoic, and 12-hydroxystearic and
mixtures of such acids.
[0075] The esters produced include all the appropriate conjugate
mono and diesters of 1,3 propanediol using the described organic
acids. Some esters in particular that are produced include
propanediol distearate and monostearate, propandiol dilaurate and
monolaurate, propanediol dioleate and monooleate, propanediol
divalerate and monovalerate, 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 all mixtures
thereof.
[0076] In particular, the esters produced include: propanediol
distearate and monostearate, propanediol dioleate and monooleate,
propanediol dicaprylate and monocaprylate, propanediol dimyristate
and monomyristate, and all mixtures thereof.
[0077] Generally 1,3-propanediol can be contacted, preferably in
the presence of an inert gas reacted with a fatty acid or mixture
of fatty acids or salts of fatty acids in the absence or presence
of a catalyst or mixture of two or more catalysts, at temperatures
ranging from 25.degree. C. to 400.degree. C.
[0078] During the contacting, water is formed and can be removed in
the inert gas stream or under vacuum to drive the reaction
complete. Any volatile byproducts can be removed similarly. When
the reaction is complete, the heating can be stopped and
cooled.
[0079] The catalyst can be removed preferably by dissolving and
removing in deionized water. If catalyst can be removed by treating
with deionized water, the reaction mixture is treated with aqueous
solutions of acid or base to forms salts and removing the salts
either by washing or filtering.
[0080] Further purification to obtain high purity fatty esters,
preferably for pharmaceutical application can be carried out by
dissolving in a solvent that dissolves fatty ester easily at higher
temperatures and least at lower temperatures and recrystallyzing
with or without addition of additional solvent at low
temperatures.
[0081] The catalyst can be an acid for non-limiting examples,
sulfuric acid, or p-toluene sulfonic acid. The catalyst can also be
a base, for non-limiting example, sodium hydroxide. The catalyst
can also be a salt, for non-limiting example, potassium acetate.
The catalyst can also be an alkoxide, for non-limiting example,
titanium tetraisopropoxide. The catalyst can also be a
heterogeneous catalyst, for non-limiting examples: zeolite,
heteropolyacid, amberlyst, or ion exchange resin. The catalyst can
also be a metal salt, for non-limiting examples, tin chloride, or
copper chloride, The catalyst can also be an enzyme, such as those
known in the art. The catalyst can also be an organic acid, for a
non-limiting example, formic acid. Finally the catalyst can also be
an organometalic compound, for non-limiting example,
n-butylstannoic acid.
[0082] This process can be carried out in the presence or absence
of a solvent. If a solvent is not necessary to facilitate the
production of fatty ester, it is preferred that the process is
carried out in the absence of solvent.
[0083] The process can be carried out at atmospheric pressure or
under vacuum or under pressurized conditions. ##STR1##
[0084] Where R1 and R2 is a hydrocarbon, preferably with a carbon
chain length of about 1 to about 40. Such hydrocarbons can be
saturated or unsaturated, substituted or unsubstituted, linear,
branched, cyclic or aromatic The carbon in R1 and R2 is between
about 1 an about 40 carbons each.
[0085] M is hydrogen, an alkali metal or an alkyl group.
##STR2##
[0086] Where R1 is a hydrocarbon, preferably with a carbon chain
length of about 1 to about 40. Such hydrocarbons can be saturated
or unsaturated, substituted or unsubstituted, linear, branched,
cyclic or aromatic. M is hydrogen, an alkali metal or an alkyl
group.
[0087] Compositions in accordance with the invention comprise
esters in which R1 has one or more functional groups selected from
the group consisting of alkene, amide, amine, aryl, carbonyl,
carboxylic acid, halide, hydroxyl groups, ether, alkyl ether,
sulfate and ethersulfate. The esters can have the formula
R1-C(.dbd.O)--O--CH2-CH2-CH2-O--C(.dbd.O)--R2, wherein both R1 and
R2 are linear, branched, cyclic or aromatic. The carbon number in
the chains or in the cyclic or aromatic groups, between about 1 an
about 40 carbons. R1 and R2 can have one or more functional groups
selected from the group consisting of alkene, amide, amine, aryl,
carbonyl, carboxylic acid, halide, hydroxyl groups, ether, alkyl
ether, sulfate and ethersulfate. Additionally, R1 and R2 can be the
same carbon chain, cyclic or aromatic group in the case of a
diester.
[0088] Any molar ratio of diol to carboxylic acid or its salt or
its ester can be used. The preferred range of the diol to
carboxylic acid is from about 1:3 to about 2:1. This ratio can be
adjusted to shift the favor of the reaction from monoester
production to diester production. Generally, to favor the
production of diesters slightly more than about a 1:2 ratio is
used; whereas to favor the production of monoesters about a 1:1
ratio is used. In general, if the diester product is desired over
the monoester the ratio of diol to dicarboxylic acid can range from
about 1.01:2 to about 1.1:2; however if the monoester is desired a
range of ratios from about 1.01:1 to about 2:1 is used.
[0089] The catalyst content for the reaction can be from 1 ppm to
60 wt % of the reaction mixture, preferably from 10 ppm to 10 wt %,
more preferably from 50 ppm to 2 wt % of the reaction mixture.
[0090] The product may contain diesters, monoesters or combination
diesters and monoesters and small percentage of unreacted acid and
diol depending on the reaction conditions. Unreacted diol can be
removed by washing with deionized water. Unreacted acid can be
removed by washing with deionized water or aqueous solutions having
base or during recrystallization.
[0091] Any ester of 1,3-propanediol can be made or used in
accordance with the present invention. Short, middle and long chain
monoesters and diesters of the 1,3-propanediol can be made.
Specifically those acids containing between about 1 and about 36
carbons in the alkyl chain can be produced. More specifically, the
following monoesters and diesters can be produced: propanediol
distearate (monostearate and the mixture), propandiol dilaurate
(monolaurate and the mixture), propanediol dioleate (monooleate and
the mixture), propanediol divalerate (monovalerate and the
mixture), propanediol dicaprylate (monocaprylate and the mixture),
propanediol dimyristate (monomyristate and the mixture),
propanediol dipalmitate (monopalmitate and the mixture),
propanediol dibehenate (monobehenate and the mixture), propanediol
adipate, propanediol maleate, propanediol dibenzoate, and
propanediol diacetate.
[0092] Compositions comprising an ester of 1,3-propanediol, wherein
the 1,3-propanediol is biologically derived contain biobased carbon
from the biologically derived 1,3-propanediol. Accordingly, these
esters can have varying amounts of biobased carbon, depending on
what acids are used in the esterification process. The compositions
can include esters that have at least 1% biobased carbon, 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% biobased carbon, or 100% biobased
carbon depending on the length of the carbon chain of the organic
acid used to produce the ester, whether the ester is a diester or a
monoester, and whether the organic acid contained biobased carbon
or fossil-fuel based carbon.
[0093] These compositions comprising an ester of 1,3-propanediol
can be produced by providing biologically produced 1,3-propanediol;
contacting the 1,3-propanediol with an organic acid, wherein the
ester is produced; and recovering the ester. The 1,3-propanediol
provided can have at least 90% biobased carbon, at least 95%
biobased carbon, or 100% biobased carbon. Additionally, the
biologically-produced 1,3-propanediol provided for the process can
have at least one of the following characteristics: 1) an
ultraviolet 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 L*a*b* "b*" color value of less than about
0.15 an absorbance of 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.
[0094] The ester can also be produced by providing 1,3-propanediol
with at least 90% biobased carbon; contacting the 1,3-propanediol
with an acid, forming the ester; and recovering the ester. The
contacting of the 1,3-propanediol with an acid can be done in the
presence of a catalyst to facilitate the esterification reaction,
and the catalyst can be categorized as a member of one or more of
the acids, bases, salts, alkoxides, heterogeneous, catalysts, metal
salts, enzymes, organic acids, and organometalic compounds.
Specifically, the catalyst can be sulfuric acid, or p-toluene
sulfonic acid, sodium hydroxide, potassium acetate, titanium
tetraisopropoxide, zeolite, heteropolyacid, amberlyst, ion exchange
resin, tin chloride, or copper chloride, formic acid, or
n-butylstannoic acid.
[0095] Food and feed compositions disclosed herein comprise esters
of 1,3-propanediol as greater than 0% up to 20% of the composition.
The 1,3-propanediol ester comprises substantially all of the
binder, defoaming agent, emulsifier, flavoring, formulation aid,
lubricant, stabilizer, thickener, gelling agent, surface active
agent, or whipping agent of the food composition.
[0096] A sample of biologically-derived 1,3-propanediol was
submitted to Iowa State University for biobased content analysis
using ASTM method D 6866-05. The results received from Iowa State
University demonstrated that the above sample was 100% bio-based
content.
[0097] Esters of 1,3-propanediol are appropriate substitutes in
food compositions for C8-C14 propylene glycol fatty acids esters
and propylene glycol alginate, which are commonly used in food
products. Propylene glycol fatty acid esters in food compositions
serve dual purposes as both an antimicrobial active and a vehicle
without the need of another aqueous or non-aqueous solvent as a
separate vehicle.
[0098] Propylene Glycol Alginate is useful as a defoaming agent,
emulsifier, foaming agent, gelling agent, stabilizer, suspending
agent, thickener, flavoring agent, surface active agent, and
whipping agent in food compositions. Similarly, appropriate esters
of 1,3-propanediol are useful as an emulsifier, foaming agent,
gelling agent, stabilizer, suspending agent, thickener, flavoring
agent, surface active agent, and whipping agent in food
compositions.
[0099] Propylene glycol mono-and diesters fats and fatty Acids are
useful as an emulsifier, defoaming agent, stabilizer, suspending
agent, lubricant, binder, and whipping agent. The corresponding
esters of 1,3-propanediol are similarly useful as an emulsifier,
defoaming agent, stabilizer, suspending agent, lubricant, binder,
and whipping agent in food compositions.
[0100] The specific propylene glycol esters, dibenzoate, stearate,
and laurate are used as adhesives. The corresponding esters of
1,3-propanediol are also useful as adhesives.
[0101] Esterified alginate has special function in emulsifying,
stabilizing, thickening and decentralizing, which allow it to be
widely used in juice, salad dressing s, emulsified essence, beer,
lactobacillus drinks, cosmetics, instant noodles, condiments, soy
sauce, and bittern oil industry. It is unmatchable in its
stabilization and refreshing scent, which is useful as an additive
for acidic protein drinks. Alginic esters of 1,3 propanediol have
similar properties, such that these esters perform similarly in
these food compositions.
[0102] The 1,3 propanediol alginate esters are useful as an
additive in beer. The 1,3 propanediol alginate esters improve the
performance of bubble, increase bubble's adhesive ability and
improve beer's appearance. The 1,3 propanediol alginate esters
counteract some components which can eliminate bubble in beer. The
1,3 propanediol alginate esters also increase the life span of the
bubble, and make bubbles more exquisite.
[0103] In the dairy industry, 1,3 propanediol alginate esters can
be used to improve texture and taste in yogurt. These
characteristics maintain even in a product containing a low content
of milk-solid. The 1,3 propanediol alginate esters can effectively
prevent product from forming a coarse surface and provide a smooth
and glossy exterior to the product. The 1,3 propanediol alginate
esters can fully mix with other additives and can be used in a wide
PH range. Gentle mixing can mix 1,3 propanediol alginate esters
evenly into yogurt. The 1,3 propanediol alginate esters are stabile
in heating processes, and can be used as stabilizer and
emulsifier.
[0104] Some specific uses of 1,3 propanediol alginate esters in
food products include:
[0105] 1. as a stabilizer in frozen dairy desserts, in fruit and
water ices, and in confections and frostings at a level not to
exceed 0.5 percent by weight of the finished product;
[0106] 2. as an emulsifier, flavoring adjuvant, stabilizer, or
thickener in baked goods at a level not to exceed 0.5 percent by
weight of the finished product;
[0107] 3. as an emulsifier, stabilizer, or thickener in cheeses at
a level not to exceed 0.9 percent by weight of the finished
product;
[0108] 4. as an emulsifier, stabilizer, or thickener in fats and
oils at a level not to exceed 1.1 percent by weight of the finished
product;
[0109] 5. as an emulsifier, stabilizer, or thickener in gelatins
and puddings at a level not to exceed 0.6 percent by weight of the
finished product;
[0110] 6. as a stabilizer or thickener in gravies and in sweet
sauces at a level not to exceed 0.5 percent by weight of the
finished product;
[0111] 7. as a stabilizer in jams and jellies at a level not to
exceed 0.4 percent by weight of the finished product;
[0112] 8. as an emulsifier, stabilizer, or thickener in condiments
and relishes at a level not to exceed 0.6 percent by weight of the
finished product;
[0113] 9. as a flavoring adjunct or adjuvant in seasonings and
flavors at a level not to exceed 1.7 percent by weight of the
finished product;
[0114] 10. as an emulsifier, flavoring adjuvant, formulation aid,
stabilizer or thickener, or surface active agent in other foods,
where applicable, at a level not to exceed 0.3 percent by weight of
the finished product.
[0115] The following table provides a listing of food categories in
which alginate esters of 1,3-propanediol can be used and the
function of the alginate esters of 1,3-propanediol in those food
compositions, as well as the FDA approved approximate upper limit
on the amount by weight of the alginate esters of 1,3-propanediol
in the food composition. TABLE-US-00001 Category Function Limit
Frozen dairy desserts, fruit Stabilizer 0.5% and water ices, and
confections and frostings Baked goods Emulsifier, Flavoring,
Stabilizer 0.5% or Thickener Cheeses Emulsifier, Stabilizer or
Thickener 0.9% Fats and oils Emulsifier, Stabilizer or Thickener
1.1% Gelatins and puddings Emulsifier, Stabilizer or Thickener 0.6%
Gravies and in sweet sauces Stabilizer or Thickener 0.5% Jams and
jellies Stabilizer 0.4% Condiments and relishes Emulsifier,
Stabilizer or Thickener 0.6% Seasonings and flavors Flavoring 1.7%
Other (beer, fruit juices, lactic Emulsifier, Flavoring,
Formulation 0.3% acid drinks, instant foods) Aid, Stabilizer or
Thickener, or Surface Active Agent
[0116] The following table provides a listing of specific foods in
which non-alginate esters of 1,3-propanediol can be used, as well
as the approximate upper limit on the amount by weight of the
alginate esters of 1,3-propanediol in the food composition.
TABLE-US-00002 Food Category Limit % Fruit fillings for pastries
10.00% Beverage whiteners 4.00% Cereal and starch based desserts
(e.g., rice pudding, tapioca 4.00% pudding) Fat emulsions maily of
type oil-in-water, including mixed 4.00% and/or flavored products
based on fat emulsions Confectionery including hard and soft candy,
nougats, etc. 4.00% other than food categories 05.1, 05.3 and 05.4
Chewing gum 4.00% Vegetable oils and fats 4.00% Blends of butter
and margarine 4.00% Dietetic formulae for slimming purposes and
weight reduction 3.00% Cream analogues 2.00% Dietetic foods
intended for special medical purposes 2.00% (excluding products of
food category 13.1) Emulsions containing less than 80% fat 2.00%
Lard, tallow, fish oil, and other animal fats 1.50% Bakery wares
1.00% Dairy-based drinks, flavored and/or fermented (e.g., 1.00%
chocolate milk, cocoa, eggnog, drinking yoghurt, whey-based drinks)
Dairy-based desserts (e.g., pudding, fruit or flavored 1.00%
yoghurt) Water-based flavored drinks, including "sport," "energy,"
or 0.50% "electrolyte" drinks and particulated drinks Milk and
cream powder analogues 0.50% Fruit-based desserts, including
fruit-flavored water-based 0.50% desserts Decorations (e.g., for
fine bakery wares), toppings (non-fruit) 0.50% and sweet sauces
Egg-based desserts (e.g., custard) 0.50% Margarine and similar
products 0.50% Edible ices, including sherbet and sorbet 0.50%
Vegetable (including mushrooms and fungi, roots and tubers, 0.50%
pulses and legumes, and aloe vera), seaweed, and nut and seed pulps
and reparations (e.g., vegetable desserts and sauces, candied
vegetables) other than food category 04.2.2.5 Cocoa mixes (powders)
and cocoa mass/cake 0.50% Other sugars and syrups (e.g., xylose,
maple syrup, sugar 0.50% toppings) Fat-based desserts excluding
dairy-based dessert products of 0.10% food category 01.7 Fruit
preparations, including pulp; purees, fruit toppings and 0.05%
coconut milk
[0117] A "food composition" includes a food or food component
consisting of one or more ingredients. Further, a food composition
includes human food, substances migrating to food from food-contact
articles, beverages, pet food, and animal feed compositions.
[0118] An "ingredient" includes any ingredient that can be used in
a food composition. It is preferred that an ingredient be of
appropriate food grade; that it be prepared and handled as a food
ingredient; and that the quantity of the ingredient added to food
does not exceed the amount reasonably required to accomplish the
intended physical, nutritional, or other technical effect in
food.
[0119] Food compositions of the invention can comprise from 0.0001%
to 20% 1,3 propanediol ester by weight, and more preferably from
about 0.1% to about 10% 1,3 propanediol ester by weight. A typical
food composition formulation of the present invention could include
0.5% to 5% 1,3 propanediol ester.
[0120] In the food compositions of the invention, the 1,3
propanediol ester can be a dough strengthener, emulsifier,
emulsifier salt, flavoring agent, flavoring adjuvant, formulation
aid, processing aid, solvent, vehicle, stabilizer, thickener,
surface-active agent, texturizer, gelling agent, gelatinizer,
lubricant, binder, foaming, or defoaming agent.
[0121] "Dough strengtheners" are generally defined as substances
used to modify starch and gluten, thereby producing a more stable
dough, including the applicable effects listed by the National
Academy of Sciences/National Research Council under "dough
conditioner."
[0122] "Emulsifiers and emulsifier salts" are generally defined as
substances which modify surface tension in the component phase of
an emulsion to establish a uniform dispersion or emulsion.
[0123] "Flavoring agents and adjuvants" are generally defined as
substances added to impart or help impart a taste or aroma in
food.
[0124] "Formulation aids" are generally defined as substances used
to promote or produce a desired physical state or texture in food,
including carriers, binders, fillers, plasticizers, film-formers,
and tableting aids, etc.
[0125] "Processing aids" are generally defined as substances used
as manufacturing aids to enhance the appeal or utility of a food or
food component, including clarifying agents, clouding agents,
catalysts, flocculents, filter aids, and crystallization
inhibitors, etc.
[0126] "Solvents and vehicles" are generally defined as substances
used to extract or dissolve another substance.
[0127] "Stabilizers and thickeners" are generally defined as
substances used to produce viscous solutions or dispersions, to
impart body, improve consistency, or stabilize emulsions, including
suspending and bodying agents, setting agents, jellying agents, and
bulking agents, etc.
[0128] "Surface-active agents" are generally defined as substances
used to modify surface properties of liquid food components for a
variety of effects, other than emulsifiers, but including
solubilizing agents, dispersants, foods, wetting agents,
rehydration enhancers, whipping agents, foaming agents, and
defoaming agents, etc.
[0129] "Texturizers" are generally defined as substances which
affect the appearance or feel of the food.
[0130] Below is a non-limiting listing of food compositions of the
invention comprising 1,3 propanediol esters:
[0131] Fruit filling for pastries containing up to about 10% 1,3
propanediol ester by weight.
[0132] Beverage whiteners containing up to about 4% 1,3 propanediol
ester by weight.
[0133] Cereal and starch based desserts (eg. Rice pudding, tapioca
pudding) containing up to about 4% 1,3 propanediol ester by
weight.
[0134] Fat emulsions mainly of type oil-in-water, including mixed
and/or flavoured products based on fat emulsions containing up to
about 5% 1,3 propanediol ester by weight.
[0135] Confectionery including hard and soft candy, nougats, etc.,
other than food categories 05.1, 05.3, and 05.4 containing up to
about 4% 1,3 propanediol ester by weight.
[0136] Chewing Gum containing up to about 4% 1,3 propanediol ester
by weight.
[0137] Vegetable Oils and Fats containing up to about 4% 1,3
propanediol ester by weight.
[0138] Blends of butter and margarine containing up to about 4% 1,3
propanediol ester by weight.
[0139] Dietetic formulae for slimming purposes and weight reduction
containing up to about 3% 1,3 propanediol ester by weight.
[0140] Cream Analogues containing up to about 2% 1,3 propanediol
ester by weight.
[0141] Dietetic foods intended for special medical purposes
(excluding products of food category 13.1) containing up to about
2% 1,3 propanediol ester by weight.
[0142] Emulsions containing less than 80% fat containing up to
about 2% 1,3 propanediol ester by weight.
[0143] Lard, tallow, fish oil, and other animal fats containing up
to about 1.5% 1,3 propanediol ester by weight.
[0144] Bakery wares containing up to about 1% 1,3 propanediol ester
by weight.
[0145] Dairy-based drinks, flavored and/or fermented (eg chocolate
milk, cocoa, eggnog, drinking yogurt, whey-based drinks) containing
up to about 1% 1,3 propanediol ester by weight.
[0146] Water-based flavored drinks, including "sport", "energy", or
"electrolyte" drinks and particulated drinks containing up to about
0.5% 1,3 propanediol ester by weight.
[0147] Milk and Cream powder analogues containing up to about 0.5%
1,3 propanediol ester by weight.
[0148] Fruit based desserts, including fruit-flavored water-based
desserts containing up to about 0.5% 1,3 propanediol ester by
weight.
[0149] Decorations (eg for fine bakery wares), toppings (non-fruit)
and sweet sauces containing up to about 0.5% 1,3 propanediol ester
by weight.
[0150] Egg-based desserts containing up to about 0.50% 1,3
propanediol ester by weight.
[0151] Margarine and similar products containing up to about 0.5%
1,3 propanediol ester by weight.
[0152] Edible ices, including sherbert and sorbet containing up to
about 0.5% 1,3 propanediol ester by weight.
[0153] Vegetable (including mushrooms and fungi, roots and tubers,
pulses and legumes, and aloe vera), seaweed, and nut and seed pulps
and reparations (e.g., vegetable desserts and sauces, candied
vegetables) other than food category 04.2.2.5 containing up to
about 0.5% 1,3 propanediol ester by weight.
[0154] Cocoa mixes (powders) and cocoa mass/cake containing up to
about 0.5% 1,3 propanediol ester by weight.
[0155] Other sugars and syrups (eg. Xylose, maple sugar, sugar
toppings) containing up to about 0.5% 1,3 propanediol ester by
weight.
[0156] Fat based desserts excluding dairy based dessert products of
food category 01.7 containing up to about 0.1% 1,3 propanediol
ester by weight.
[0157] Fruit preparations, including pulp, purees, fruit toppings
and coconut milk containing up to about 0.05% 1,3 propanediol ester
by weight.
[0158] All of the compositions and methods disclosed and claimed
herein can be made and executed without undue experimentation in
light of the present disclosure. While the compositions and methods
of the present disclosure have been described in terms of preferred
embodiments, it will be apparent to those of skill in the art that
variations may be applied to the compositions and methods and in
the steps or in the sequence of steps of the method described
herein without departing from the concept, spirit, and scope of the
invention. More specifically, it will be apparent that certain
agents, which are chemically related, may be substituted for the
agents described herein while the same or similar results would be
achieved. All such similar substitutes and modifications apparent
to those skilled in the art are deemed to be within the spirit,
scope, and concept of the invention as defined by the appended
claims.
EXAMPLES
[0159] The present invention is further defined in the following
Examples. These Examples, while indicating preferred embodiments of
the invention, are given by way of illustration only. From the
above discussion and these Examples, one skilled in the art can
ascertain the essential characteristics of this invention, and
without departing from the spirit and scope thereof, can make
various changes and modifications of the invention to adapt it to
various usages and conditions.
[0160] The meaning of abbreviations used is as follows: "min" means
minute(s), "sec" means second(s), "h" means hour(s), ".mu.L" means
microliter(s), "mL" means milliliter(s), "L" means liter(s), "nm"
means nanometer(s), "mm" means millimeter(s), "cm" means
centimeter(s), ".mu.m" means micrometer(s), "mM" means millimolar,
"M" means molar, "mmol" means millimole(s), ".mu.mole" means
micromole(s), "g" means gram(s), ".mu.g" means microgram(s), "mg"
means milligram(s), "g" means the gravitation constant, "rpm" means
revolutions per minute, "SEM" means standard error of the mean,
"vol %" means volume percent and "NMR" means nuclear magnetic
resonance.
[0161] The meaning of abbreviations used is as follows "% wt."
means percent by weight; "qs" means as much as suffices; "EDTA"
means ethylenediamine tetraacetate; ".degree. C." means degrees
Centigrade; ".degree. F." is degrees Fahrenheit, "Bio--PDO" means
biologically-derived 1,3-propanediol; "ppm" is parts per million;
"AU" is absorbance unit; "nm" is nanometer(s); "GC" is gas
chromatograph; "APHA" is American Public Health Association; "cps"
is centipoise; "f/t" is freeze/thaw; "mPas" is milliPascal seconds;
"D.I." is deionized.
[0162] The present invention is further defined in the following
Examples. It should be understood that these Examples, while
indicating preferred embodiments of the invention, are given by way
of illustration only. From the above discussion and these Examples,
one skilled in the art can ascertain the essential characteristics
of this invention, and without departing from the spirit and scope
thereof, can make various changes and modifications of the
invention to adapt it to various uses and conditions.
[0163] The meaning of abbreviations used is as follows "% wt."
means percent by weight; "qs" means as much as suffices; "EDTA"
means ethylenediamine tetraacetate; ".degree. C." means degrees
Centigrade; ".degree. F." is degrees Fahrenheit, "Bio--PDO" means
biologically-derived 1,3-propanediol; "ppm" is parts per million;
"AU" is absorbance unit; "nm" is nanometer(s); "GC" is gas
chromatograph; "APHA" is American Public Health Association; "cps"
is centipoise; "f/t" is freeze/thaw; "mPas" is millipascal seconds;
"D.I." is deionized.
General Methods:
[0164] Standard recombinant DNA and molecular cloning techniques
used in the Examples are well known in the art and are described by
Sambrook, J., Fritsch, E. F. and Maniatis, T., Molecular Cloning: A
Laboratory Manual, Cold Spring Harbor Laboratory Press, Cold Spring
Harbor, N.Y., 1989, by T. J. Silhavy, M. L. Bennan, and L. W.
Enquist, Experiments with Gene Fusions, Cold Spring Harbor
Laboratory, Cold Spring Harbor, N.Y., 1984, and by Ausubel, F. M.
et al., Current Protocols in Molecular Biology, Greene Publishing
Assoc. and Wiley-Interscience, N.Y., 1987.
[0165] Materials and methods suitable for the maintenance and
growth of bacterial cultures are also well known in the art.
Techniques suitable for use in the following Examples may be found
in Manual of Methods for General Bacteriology, Phillipp Gerhardt,
R. G. E. Murray, Ralph N. Costilow, Eugene W. Nester, Willis A.
Wood, Noel R. Krieg and G. Briggs Phillips, eds., American Society
for Microbiology, Washington, D.C., 1994, or by Thomas D. Brock in
Biotechnology: A Textbook of Industrial Microbiology, Second
Edition, Sinauer Associates, Inc., Sunderland, Mass., 1989.
[0166] All reagents, restriction enzymes and materials used for the
growth and maintenance of bacterial cells were obtained from
Aldrich Chemicals (Milwaukee, Wis.), BD Diagnostic Systems (Sparks,
Md.), Life Technologies (Rockville, Md.), or Sigma Chemical Company
(St. Louis, Mo.), unless otherwise specified.
[0167] Glycerol used in the production of 1,3-propanediol was
obtained from J. T. Baker Glycerin USP grade, Lot 325608 and
G19657.
[0168] Differential Scanning Calorimetry: DSC thermograms were
recorded using Universal V3 1A TA instrument under constant stream
of nitrogen with a heating and cooling rate of 10.degree.
C./min.
[0169] NMR: 1H NMR spectra were recorded on Bruker DRX 500 using
XWINNMR version 3.5 software. Data was acquired using a 90 degree
pulse (p1) and a 30 second recycle delay (d1). Samples were
dissolved in deuterated chloroform and nondeuterated chloroform was
used as internal standard.
Isolation and Identification Bio-PDO
[0170] The conversion of glycerol to bio-PDO was monitored by HPLC.
Analyses were performed using standard techniques and materials
available to one of skill in the art of chromatography. One
suitable method utilized a Waters Maxima 820 HPLC system using UV
(210 nm) and R1 detection. Samples were injected onto a Shodex
SH-1011 column (8 mm.times.300 mm, purchased from Waters, Milford,
Mass.) equipped with a Shodex SH-1011P precolumn (6 mm.times.50
mm), temperature controlled at 50.degree. C., using 0.01 N H2SO4 as
mobile phase at a flow rate of 0.5 mL/min. When quantitative
analysis was desired, samples were prepared with a known amount of
trimethylacetic acid as external standard. Typically, the retention
times of glycerol (R1 detection), 1,3-propanediol (R1 detection),
and trimethylacetic acid (UV and R1 detection) were 20.67 min 26.08
min, and 35.03 min, respectively.
[0171] Production of bio-PDO was confirmed by GC/MS. Analyses were
performed using standard techniques and materials available to one
of skill in the art of GC/MS. One suitable method utilized a
Hewlett Packard 5890 Series II gas chromatograph coupled to a
Hewlett Packard 5971 Series mass selective detector (EI) and a
HP-INNOWax column (30 m length, 0.25 mm i.d., 0.25 micron film
thickness). The retention time and mass spectrum of 1,3-propanediol
generated from glycerol were compared to that of authentic
1,3-propanediol (m/e: 57, 58).
Production of Bio-Based Monoesters and Diesters from Bio-Produced
1,3-Propanediol.
[0172] Monoesters and diester of bio-produced 1,3-propandiol may be
produced by combining bioPDO with organic acid. The combination is
to be preformed in dry conditions under heat and prolong agitation
with a selected catalyst. The ratio of monoester to diester
produced will vary according to the molar ratio of acid to bioPDO
and the selection of catalyst.
[0173] The production of esters was confirmed using .sup.1H nuclear
magnetic resonance. Analyses were performed using standard
techniques and materials available to one of skill in the art of
.sup.1H NMR.
[0174] Proton Nuclear Magnetic Resonance (.sup.1H NMR) Spectroscopy
is a powerful method used in the determination of the structure of
unknown organic compounds. It provides information concerning: the
number of different types of hydrogens present in the molecule, the
electronic environment of the different types of hydrogens and the
number of hydrogen "neighbor" a hydrogen has.
[0175] The hydrogens bound to carbons attached to electron
withdrawing groups tend to resonate at higher frequencies from TMS,
tetramethylsilane, a common NMR standard. The position of where a
particular hydrogen atom resonates relative to TMS is called its
chemical shift (8). Typical chemicals shifts of fatty ester are as
follows.
[0176] .delta.=0.88 for terminal CH.sub.3
[0177] .delta.=1.26, 1.61 and 1.97 for methylene groups of
(--CH.sub.2--CH.sub.2--CH.sub.2), (CH.sub.2--CH.sub.2--C.dbd.O) and
(O--CH.sub.2--CH.sub.2--CH.sub.2--O) respectively,
[0178] .delta.=2.28 for methylene group adjustment to ester
(CH.sub.2--C.dbd.O)
[0179] .delta.=4.15 for ester (C(.dbd.O)--O--CH.sub.2--). Proton
NMR can distinguish the protons corresponding to the end groups
(CH.sub.2--OH) (.delta.=3.7) from that of the middle ester groups
(CH.sub.2--O--C(.dbd.O)--) (.delta.=4.15 and 4.24 for diester and
monoester, respectively) and thus it is possible to identify ester
and can monitor the reaction by comparing the integral areas of
these two peaks. % .times. .times. Esterification = Combined
.times. .times. areas .times. .times. of .times. .times. peaks
.times. .times. at .times. .times. 41.5 .times. .times. and .times.
.times. 4.24 .times. 100 Combined .times. .times. areas .times.
.times. of .times. .times. peaks .times. .times. at .times. .times.
3.70 , 41.5 .times. .times. and .times. .times. 4.24 ##EQU1##
Example 1
Conversion of D-glucose to 1,3-Propanediol Under Fermentation
Conditions
[0180] E. coli strain ECL707, containing the K. pneumoniae dha
regulon cosmids pKP1 or pKP2, the K. pneumoniae pdu operon pKP4, or
the Supercos vector alone, is grown in a 5 L Applikon fermenter for
the production of 1,3-propanediol from glucose.
[0181] The medium used contains 50-100 mM potassium phosphate
buffer, pH 7.5, 40 mM (NH4)2SO4, 0.1% (w/v) yeast extract, 10 .mu.M
CoCl2, 6.5 .mu.M CuCl2, 100 .mu.M FeCl3, 18 .mu.M FeSO4, 5 .mu.M
H3BO3, 50 .mu.M MnCl2, 0.1 .mu.M Na2MoO4, 25 .mu.M ZnCl2, 0.82 mM
MgSO4, 0.9 mM CaCl2, and 10-20 g/L glucose. Additional glucose is
fed, with residual glucose maintained in excess. Temperature is
controlled at 37.degree. C. and pH controlled at 7.5 with 5N KOH or
NaOH. Appropriate antibiotics are included for plasmid maintenance.
For anaerobic fermentations, 0.1 vvm nitrogen is sparged through
the reactor; when the dO setpoint was 5%, 1 vvm air is sparged
through the reactor and the medium is supplemented with vitamin
B12.
[0182] Titers of 1,3-propanediol (g/L) range from 8.1 to 10.9.
Yields of bio-PDO (g/g) range from 4% to 17%.
Example 2
Purification of Biosourced 1,3-Propanediol
[0183] Published U.S. Patent Application No. 2005/0069997 discloses
a process for purifying 1,3-propanediol from the fermentation broth
of a cultured E. coli that has been bioengineered to synthesize
1,3-propanediol from sugar. The basic process entails filtration,
ion exchange and distillation of the fermentation broth product
stream, preferably including chemical reduction of the product
during the distillation procedure.
[0184] 1,3-Propanediol, produced as recited in Example 1, was
purified, by a multistep process including broth clarification,
rotary evaporation, anion exchange and multiple distillation of the
supernatant.
[0185] 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 MW
membrane. The clarified broth processed in a large rotary
evaporator. Approximately 46 pounds of feed material (21,000 grams)
were processed to a concentrated syrup. A 60 ml portion of syrup
was placed in the still pot of a 1'' diameter distillation column.
Distillation was conducted at a vacuum of 25 inches of mercury. A
reflux ratio of approximately 1 was used throughout the
distillation. Several distillate cuts were taken, the central of
which received further processing. The material was diluted with an
equal volume of water, the material was loaded onto an anion
exchange column (mixed bed, 80 grams of NM-60 resin), which had
been water-washed. Water was pumped at a rate of 2 ml/min, with
fractions being collected every 9 minutes. Odd number fractions
were analyzed, and fractions 3 through 9 contained 3 G. The
fractions containing 3 G were collected and subjected to
microdistillation to recover several grams of pure 1,3-propanediol
monomer (which was polymerized to mono and diesters according the
methods described in Example 2-8).
Example 3
Production of Propanediol Distearate Using P-toluenesulfonic Acid
as Catalyst
[0186] To prepare propanediol distearate from biosource
1,3-propanediol and stearic acid, biosource 1,3-propanediol was
purified using methods as in examples 1 and 2. 2.58 g (0.033 moles)
of biosource 1,3-propanediol, 19.45 g (0.065 moles) of stearic acid
(Aldrich, 95%), and 0.2125 g (0.001 moles) of p-toluenesulfonic
acid (Aldrich 98.5%) were charged into glass reactor fitted with
mechanical stirrer and the reactor was flushed with dry nitrogen
gas to remove air and moisture for 15 min. Then reaction
temperature was raised to 100.degree. C. while thoroughly stirring
the reaction mixture under nitrogen flow and continued for 210
min.
[0187] After completion of the reaction, reaction mixture was
cooled to about 35.degree. C. and the product was transferred into
a beaker. The product was purified by adding 100 mL of water and
thoroughly stirring at 45-60.degree. C., to form an emulsion for 15
min. The mixture was cooled and the solid propanediol distearate
was separated by filtration.
[0188] The product was characterized by .sup.1H NMR (Nuclear
Magnetic Resonance) spectra (CDCl.sub.3 (deuterated chloroform)):
.delta.=0.88 (t, CH.sub.3--CH.sub.2, 6H), 1.26 (t,
CH.sub.2--CH.sub.2--CH.sub.2, 28H), 1.61 (t,
CH.sub.2--CH.sub.2--C.dbd.O, 4H), 1.97 (t,
--O--CH.sub.2--CH.sub.2--CH.sub.2--O, 2H), 2.28 (t,
CH.sub.2--C.dbd.O, 4H), 4.15 (t, C(.dbd.O)--O--CH.sub.2-- 4H) and
DSC (Tm=66.4.degree. C. and Tc=54.7.degree. C.), as shown in FIG.
1.
Example 4
Purity Characterizations of Biologically-Derived
1,3-Propanediol
[0189] In Table 1 below, biologically-derived 1,3-propanediol
(produced and purified as described in Published U.S. Patent
Application No. 2005/0069997) ("Bio-PDO") is compared, in several
purity aspects, to two separate commercially-obtained preparations
of chemically-produced 1,3-propanediol (Source A and B).
TABLE-US-00003 TABLE 1 Units Source A Source B Bio-PDO Total Org
Impurities ppm 570 695 80 UV Abs 220 nm, AU 0.25 1.15 0.12 UV Abs
250 nm, AU 0.123 0.427 0.017 UV Abs 275 nm AU 0.068 0.151 0.036 UV
Abs 350 nm AU 0.013 0.007 0.001 Peroxides ppm 67 43 2 CIE L*a*b*
ASTM D6290 b* 0.411 0.03 0.1 Carbonyls ppm 147 175 1
[0190] A typical profile of purity aspects are provided in Table 2
below, on a sample of biologically-produced 1,3-propanediol
purified by a process disclosed in Published U.S. Patent
Application No. 2005/0069997. TABLE-US-00004 TABLE 2 Units
1,3-Propanediol GC area % 99.992 pH, neat pH 8.22 UV Abs. @ 270 nm,
1:5 dilution AU 0.01 Color APHA 3 Color (Process Measurement)
L*a*b* b* 0.10 Water ppm 115 UV abs 220 nm neat AU 0.144 UV abs 250
nm neat AU 0.017 UV abs 275 nm neat AU 0.036 UV abs 350 nm neat AU
0.001 Peroxide ppm 2 Metals ppm <1 Sulfur ppm <1 Carbonyl ppm
1
[0191] The unit ppm of total organic impurities means parts per
million of total organic compounds in the final preparation, other
than 1,3-propanediol, as measured by a gas chromatograph with a
flame ionization detector. Results are reported by peak area. A
flame ionization detector is insensitive to water, so the total
impurity is the sum of all non 1,3-propanediol organic peaks (area
%) ratioed to the sum of all area % (1,3-propanediol included). The
term "organic materials" refers to the contaminants containing
carbon.
[0192] The tables show that the disclosed method of purification
provides for highly pure biologically derived 1,3-propanediol, as
compared to commercially-obtained preparations of
chemically-produced 1,3-propanediol.
Example 5
Production of Propanediol Distearate Using p-toluenesulfonic Acid
as Catalyst
[0193] 39.61 g (0.133 moles) of stearic acid (Aldrich, 95%), 5.05 g
(0.066 moles) of bio-source 1,3-propanediol (Bio-PDO) and 0.46 g
(0.0024 moles) of p-toluenesulfonic acid were charged into glass
reactor fitted with mechanical stirrer and the reactor was flushed
with dry nitrogen gas to remove air and moisture for 15 min. Then
reaction temperature was raised to 100.degree. C. while thoroughly
stirring the reaction mixture under nitrogen flow. When the
reaction temperature reached 100 .quadrature.C, nitrogen flow was
shut off and low vacuum was applied to remove by byproduct. The
reaction was continued for 2 h. The vacuum was stopped and product
was cooled under nitrogen flow.
[0194] The product was purified as described in Example 3 and
recrystallized as described in Example 4.
[0195] The product was characterized by 1H NMR spectra (CDCl3):
.delta.=0.88 (t, CH3-CH2, 6H), 1.26 (t, CH2-CH2-CH2, 28H), 1.61 (t,
CH2-CH2-C.dbd.O, 4H), 1.97 (t, --O--CH2-CH2-CH2-O, 2H), 2.28 (t,
CH2-C.dbd.O, 4H), 4.15 (t, C(.dbd.O)--O--CH2-4H). FIG. 4 depicts a
graph of these data.
Example 6
Production Of Propanediol Monostearate and Propanediol Distearate
Using Tin Chloride as Catalyst
[0196] 72.06 g (0.243 moles) of stearic acid (Aldrich, 95%), 9.60 g
(0.126 moles) of 1,3-propanediol and 0.25 g of SnCl2 (Aldrich 98%)
were charged into glass reactor fitted with mechanical stirrer and
the reactor was flushed with dry nitrogen gas to remove air and
moisture for 15 min. Then reaction temperature was raised to
120.degree. C. while thoroughly stirring the reaction mixture under
nitrogen flow and continued for 240 min.
[0197] After completion of the reaction, reaction mixture was
cooled and analyzed by NMR. The product contained 39 mole % of
propanediol monostearate, 19 mole % of propanediol distearate and
42 mole % 1,3-propanediol.
[0198] 1H NMR spectra (CDCl3) .delta.=0.88 (t, CH3-CH2), 1.27 (t,
CH2-CH2-CH2), 1.63 (t, CH2-CH2-C.dbd.O), 1.82, 1.87 and 1.96 (t,
--O--CH2-CH2-CH2-O), 2.31 (t, CH2-C.dbd.O), 3.69 and 3.86
(t,HO--CH2-CH2-), 4.15 and 4.21 (t, C(.dbd.O)--O--CH2-). FIG. 5
depicts a graph of these data.
Example 7
Production of Propanediol Monostearate and Propanediol Distearate
Using Titanium Tetraisopropoxide as Catalyst
[0199] 35.51 g (0.119 moles) of stearic acid (Aldrich, 95%), 9.55 g
(0.125 moles) of 1,3-propanediol and 0.01 g of Ti(OC3H7)4 (Aldrich,
99.99%) were charged into glass reactor fitted with mechanical
stirrer and the reactor was flushed with dry nitrogen gas to remove
air and moisture for 15 min. Then reaction temperature was raised
to 170.degree. C. while thoroughly stirring the reaction mixture
under nitrogen flow and continued for 240 min. Then the reaction
was continued under vacuum for another 30 min. The vacuum was
stopped and product was cooled under nitrogen flow and analyzed by
NMR.
[0200] The product has 36 mole % propanediol monostearate and 64
mole % propanediol distearate.
[0201] 1H NMR spectra (CDCl3) .delta.=0.88 (t, CH3-CH2), 1.27 (t,
CH2-CH2-CH2), 1.60 (t, CH2-CH2-C.dbd.O), 1.87 and 1.96 (t,
--O--CH2-CH2-CH2-O), 2.31 (t, CH2-C.dbd.O), 3.70 (t,HO--CH2-CH2-),
4.15 and 4.24 (t, C(.dbd.O)--O--CH2-). FIG. 6 depicts a graph of
these data.
Example 8
Production of Propanediol Monostearate and Propanediol Distearate
Using Potassium Acetate as Catalyst
[0202] 39.72 g (0.133 moles) of stearic acid (Aldrich, 95%), 10.12
g (0.133 moles) of bio-source 1,3-propanediol (Bio-PDO) and 2.47 g
(0.025 moles) of potassium acetate (Aldrich, 99%) were charged into
glass reactor fitted with mechanical stirrer and the reactor was
flushed with dry nitrogen gas to remove air and moisture for 15
min.
[0203] Then reaction temperature was raised to 130.degree. C. while
thoroughly stirring the reaction mixture under nitrogen flow. The
reaction was continued for 4 h under nitrogen flow. Then the
nitrogen flow was shut off and vacuum was applied for 10 min before
stopping the reaction. The obtained product was analyzed without
further purification.
[0204] NMR analysis confirmed the product contained 64.7 mole % of
propanediol monostearate, 9.7% mole % of Propanediol distearate and
25.6 mole % 1,3 Propanediol.
[0205] 1H NMR spectra (CDCl.sub.3) .delta.=0.88 (t, CH3-CH2), 1.27
(t, CH2-CH2-CH2), 1.63 (t, CH2-CH2-C.dbd.O), 1.82, 1.87 and 1.96
(t, --O--CH2-CH2-CH2-O), 2.31 (t, CH2-C.dbd.O), 3.70 and 3.86
(t,HO--CH2-CH2-), 4.15 and 4.24 (t, C(.dbd.O)--O--CH2-). FIG. 7
depicts a graph of these data.
Example 9
[0206] Bread rolls are made for evaluation of the present invention
according to the recipes as follows: TABLE-US-00005 Ingredient 1A
(Comparative) % 1B % 1C % Flour 57 56.9 56.8 Water 29.28 29.28
29.28 Vegetable Oil 5.5 5.5 5.5 Yeast 1.2 1.2 1.2 Sugar 5 5 5 Salt
0.95 0.95 0.95 Whey solids 0.77 0.77 0.77 DATEM 0.3 0.3 0.3 1,3
propanediol ester 0.0 0.1 0.2
Example 10
[0207] Biscuits are made for evaluation of the present invention
according to the recipes as follows: TABLE-US-00006 Ingredient 2A
(Comparative) % 2B % 2C % Flour 45.32 45.27 45.22 Water 28 28 28
Buttermilk solids 3 3 3 Xanthan 0.13 0.13 0.13 Shortening 14 14 14
Salt 1.3 1.3 1.3 Chemical Leaveners 2.25 2.25 2.25 Sugar 5.5 5.5
5.5 Dough conditioner 0.5 0.5 0.5 1,3 propanediol ester 0.0 0.05
0.1
Example 11
[0208] Beverage emulsion stabilizers are made for evaluation of the
present invention according to the recipes as follows.sup.a:
TABLE-US-00007 2a 2b 2c 2d 2e 2f.sup.b Ingredient Water 301 343 339
317 330 328 Sodium 0.4 0.4 0.4 0.4 0.4 0.4 Benzoate Gum Arabic 56
-- -- -- -- -- 1,3 propanediol -- 14 18 -- 3 4.8 ester Starch -- --
-- 40 24 24 Citric acid 0.8 0.8 0.8 0.8 0.8 0.8 Yellow dye 6 1.75
1.75 1.75 1.75 1.75 1.75 Flavor oil 40 40 40 40 40 40 blend
Particle size (.mu.): median 0.33 0.27 0.25 0.34 0.34 0.36 mean
0.35 0.28 0.26 0.47 0.53 1.53
[0209] .sup.aAmounts given in g.
Example 12
[0210] An eggwash substitute according to the invention is prepared
according to the following recipe: TABLE-US-00008 Weight % Water 85
Modified Food Starch (wheat starch) 14 Citric Acid 0.4 Potassium
Sorbate .35 Sodium Benzoate 0.1 Xanthan Gum 0.1 1,3 propanediol
ester 0.1
Example 13
[0211] TABLE-US-00009 Aerosol compositions for animal feeds
Ingredient Weight Percent Molasses 25% Propylene Glycol 23% Soy
Lecithin 10% Water 22% 1,3 propanediol Capric/Caprylic Esters 4.5%
Flavoring 0.5% Isobutane/Propane/Butane 15%
Example 14
[0212] A powder foaming agent for use in cake mixes to improve
consistency of the batter is prepared according to the following
recipe: TABLE-US-00010 Ingredient Weight Percent 1,3 propanediol
ester 15% Lactic acid monoglyceride 15% Skim milk 10% Dextrin 10%
H2O 50%
[0213] Although the invention is illustrated and described herein
with reference to specific embodiments, the invention is not
intended to be limited to the details shown. Rather, various
modifications may be made in the details within the scope and range
of equivalents of the claims and without departing from the
invention.
* * * * *