WO2001056396A1

WO2001056396A1 - Novel synergistic solid/semi-solid organic composition and a process of preparing such a composition

Info

Publication number: WO2001056396A1
Application number: PCT/IN2000/000009
Authority: WO
Inventors: Ram Rajesekharan
Original assignee: Nagarjuna Holdings Private Limited; Indian Institute Of Science; Daniel, Jaiyanth
Priority date: 2000-02-04
Filing date: 2000-02-04
Publication date: 2001-08-09
Also published as: AU3574100A; AU2000235741B2; EP1255450A1; AU2000235741B8

Abstract

This invention relates to a novel synergistic reversible solid / semi-solid organic composition, said composition comprising (a) at least one saturated long chain fatty acid and/or its glycerol esters and (b) one or more liquid neutral organic compounds, said ingredients (a) and (b) being present in a ratio between 0.1 to 40% by weight, and a process for producing said synergistic reversible solid / semi-solid organic composition by mixing the ingredients (a) and (b) defined above in a ratio between 0.1 to 40% by weight, at a temperature between 2 to 50°C and at a pressure in the range of 200 torr to 2500 torr.

Description

NOVEL SYNERGISTIC SOLID/SEMI-SOLID ORGANIC COMPOSITION AND A PROCESS OF PREPARING SUCH A COMPOSITION

FIELD OF INVENTION:

The present invention relates to a novel synergistic solid/semi solid organic composition a process for producing such organic composition and a method of solidifying liquid neutral organic compounds using lipid modulators Preferably, the present invention provides a method of solidification, isolation, identification and/or separation of liquid neutral organic compounds and/or mixture of organic molecules or colloids Most preferabl} the invention encompasses hpid-modulated alteration of the physical properties of vegetable oils, essential oils, mineral oils and organic solvents

BACKGROUND OF THE INVENTION

In the field of organic chemistry, many of the organic compounds are in various phvsical states depending on their molecular structures and the surrounding temperatures and pressure Organic compounds are chemical compounds containing carbon atoms arranged in chains or πngs, together with smaller amounts of other elements, mainly hydrogen and oxygen These organic compounds are present either in liquid, solid or gaseous form at ambient temperature These organic compounds may be negatively or positively charged or devoid of charge In other words, it may have a deficiency or excess of electrons on a particular object, giving rise to a positive or negative charge respectively Organic compounds can be saturated or unsaturated ones These can be vegetable oils essential oils, mineral oils chemical solvents, etc Organic compounds have various phvsical properties such as color, odor, physical state, solubility, melting point, boiling point freezing point etc , and alteration of one or more of such properties are required in order to make them suitable for specific industrial usage or application In other words, modification of physical state of the organic compounds is essential/desirable for their various applications in the industry

Organic compounds include a group of compounds referred to as fatty acids, fatty alcohols and sterols which were originally found to be constituents of microbial, animal and vegetable fats and fatty oils Alternatively, the fatty acids, fatty alcohols and sterols can also be synthesized chemically The esters of fatty acids are their derivatives with alcohol

PRIOR ART

The art is rich in use of compounds isolated from Garcinia indica for several processes as described in the following patents and publications

Chen S, Wan M, Lok BN (1996) Planta Medica 62 381 Reddy SY, Prabhakar JV (1994) J Am Oil Chem Soc 71 217 Sundaram BM, Gopalakπshnan C, Subramanian S, Shankaranarayan D (1983) Planta Medica 4 59 The art is also nch in proposing kokum and mahua fats as substitutes for cocoa butter for Chocolate industry (Yasuda et al 1979, US patent No 4,157,405, Pairaud et al 1982, US patent No 4,348,432) The art is also rich in the process of conversion of vegetable oil into fat by chemical hydrogenation (Gunstone FD Harwood JL, Padley FB (1994) The Lipid Handbook (2^nd ed), Chapman and Hall, Madras) However, there is no description of altering the physical properties of any liquid neutral organic compounds such as vegetable oils, essential oils, mineral oils and organic solvents in a temperature-dependent manner using fatty acids or glycerol esters of fatty acids isolated from Garcinia indica There is no report on a process of biological conversion of liquid oils to a solid or semi-solid using lιpιd(s) isolated from plants such as Garcinia indica There is also no descπption of using free fatty acids, fatty alcohols, dicarboxyhc acids (adipic, suberic, sebacic acid), cholesterol and its derivatives to solidify, isolate, identify or separate any liquid neutral organic compound in prior art However, there are a few methods of solidifying liquid oils using fatty acyl wax esters (US Patent No 5,763,497) and paraffin wax esters (US Patent No 5,476,993) and hydroxyalkanoic acids (US Patent No 5,908,377)

US Patent 5,476,993 discloses a process of reversibly solidifying hydrocarbons for transportation and storage This process involves mixing hydrocarbons like crude oil with a hydrocarbon wax The wax is melted and heated to a temperature above the solidification temperature for the mixture and mixed with the oil The disadvantage of this process is that it employs large quantities of wax and is restricted to solidifying only crude oil that later under goes fractional distillation to separate various fractions In addition, there is no mention of the use of hydrocarbon wax to solidify edible oils, essential oils and organic solvents

Another US Patent 5,763,497, of 1998 discloses an oil-in-water type cosmetic composition comprising water, fatty acyl wax esters, and at least one of other components usable in cosmetics However, the above method is not reversible and also involves more active components In addition, this method has a restπctive application and not suitable for solidifying all kinds of oils and organic solvents

Yet another US Patent 5,908,377 of 1999 discloses a method of solidifying liquid oils without heating the liquid oil, using a solidifying agent which includes a gel-in-oil forming material and a temporarily protective mateπal for the gel-in-oil forming mateπal This method, as disclosed, has several disadvantages such as employing at least two components to prepare the solidifying agent, using hydroxysteaπc acids which are not suitable in food and related applications, etc These hydroxyalkanoic long chain fatty acids are only available in minute quantities in nature and it is totally uneconomical to isolate from natural resources for any commercial use On the other hand, these acids are verv expensive to chemically synthesize them Further, πcinoleic acid (12-hydroxy-c/.s-9- octadecenoic acid) does not exhibit the solidification property Furthermore, the above process does not envisage reversibility and is restricted to solidifying waste edible oils or waste engine oils to contain environmental pollution. In addition, the method is directed towards avoiding pollution of drains, rivers, lakes by waste edible oils and does not involve reversing the method. Moreover, this method does not result in uniform/homogenous solidification.

SUMMARY OF THE INVENTION

To over come the above problems, the present invention provides a novel synergistic solid /semi-solid organic composition comprising (a) at least one saturated long chain fatty acid and/or its glycerol esters, or at least one saturated long chain fatty alcohols, or at least one dicarboxylic acid, or at least one sterol or mixtures thereof and (b) one or more liquid neutral organic compounds, said ingredients (a) being present in a ratio between 0.1 to 40 percent by weight and the remaining part from (b); and a process for producing the reversing synergistic solid/semi-solid composition.

OBJECTS OF THE INVENTION

The main object of the invention is to provide a novel, reversible and synergistic solid/semi-solid composition.

Another object of the invention is to provide a synergistic solid /semi-solid organic composition comprising (a) at least one saturated long chain fatty acid and/or its glycerol esters, or at least one saturated long chain fatty alcohols, or at least one dicarboxylic acid, or at least one sterol or mixtures thereof and (b) one or more liquid neutral organic compounds.

One more object of the invention relates to a solidification of uncharged organic liquid by physical method which method is reversible. Yet another object of the invention relates to a process for producing a novel, reversible and synergistic solid/semi-solid composition

Still another object of the invention is to provide a reversible process for producing a novel, reversible and synergistic solid/semi-solid composition

DETAILED DESCRIPTION OF THE INVENTION

Our investigations to obtain insights into the mechanism of solid fat biosynthesis and accumulation in Garcinia indica, eventually led to the present invention Table 1 represents the analysis of fatty acid composition of Triacylglycerols (TAG) obtained from mature kokum (G. indica) seeds at 120 days after flowering The TAG contained more than 59% of stearic acid (C sub 18 0) and 35 % of oleic acid (C sub 18.1)

Table 1. Fatty Acid Composition of Triacylglycerols in Mature Seeds of G. indica

Age of Seeds Fatty Acid Composition

(Percentage by Weight)

(DAF)

C16 0 C18 0 C18 1 C18 2 C20 0

120 4 6 59 3 35 3 0 1 0 7

The solid oil from kokum seed was mixed with various neutral liquid organic compounds and the tubes were heated to melt the fat and kept at 4 deg. C after mixing It was observed that the liquid organic compounds were solidified Once the organic is solidified at 4 deg celsius it remains solid at NTP The solidified locate can be reconverted into liquid of identical nature by simple physical process. Therefore, the present solidification process does not involve any chemical reaction. The percentage of kokum fat required for such a solidification process is given in Table 2a. Table 2a. Percent Kokum Fat Required for Solidification of Organic Liquids at Four Degrees Celsius

Fractionation of kokum fat to identify the solidification principle

The lipid catalyst or the solidifying agent was purified from kokum fat using various column chromatographic procedures and C18 reverse phase High Performance Liquid Chromatography. The structure of the purified compound was elucidated

Aliquot from the purified triacylglycerol was subjected to alkaline hydrolysis, acidified and the free fatty acids were extracted with petroleum ether [Kates M (1964) J Lipid Res 5, 132- 135] The free fatty acid fraction and the water soluble deacylated fractions were used separately for solidifying vegetable oil In these experiments, petroleum ether fraction showed solidification property and the water-soluble deacylated fraction did not show vegetable oil solidifying property The hydrolyzed products were purified using HPLC (C18-reverse phase column). The purified compounds were identified as saturated fatty acids (stearic and palmitic acids) The purified saturated fatty acids were capable of solidifying liquid vegetable oils, essential oils, mineral oil and organic solvents These experiments suggested that the free fatty acids were capable of solidifying oil Alternatively, free fatty acids were obtained from kokum fat by enzymatic (lipase) hydrolysis and tested for solidifying property The free fatty acids from kokum fat showed solidifying activity

The fatty acids obtained from kokum fat were fractionated into individual fatty acids on C sub 18 reverse phase silica thin layer chromatography. Individual fatty acids were eluted from the thin layer chromatogram plates, used for solidification activity, and found to exhibit the similar property

The present invention describes a simple and a cost-effective method of altering physical properties of liquid neutral organic compounds by using one or more fatty acids their glycerol esters, fatty alcohols, dicarboxylic acids, sterols and mixtures thereof without involving chemical reactions

One embodiment of the invention provides a novel synergistic solid/semi-solid organic composition, said composition comprising (a) at least one saturated long chain fatty acid and/or its glycerol ester, or at least one saturated long chain fatty alcohol, or at least one dicarboxylic acid, or at least one sterol or mixtures thereof and (b) a liquid neutral organic compound, said ingredient (a) being present in an amount between 0 1 to 40 percent by weight

Another embodiment of the invention relates to a process for producing a novel synergistic solid/semi-solid organic composition, said process comprising mixing (a) at least one saturated long chain fatty acid and/or its glycerol ester, or at least one saturated long chain fatty alcohol, or at least one dicarboxylic acid, or at least one sterol or mixtures thereof in an amount between 0.1 to 40 percent by weight with (b) a liquid neutral organic compound It is also possible to perform the process at varying pressures with corresponding modification in respect of other parameters of the process The pressure can vary between 200 torr to 2500 torr Yet another embodiment of the invention relates to a method of solidifying liquid neutral organic compounds or their mixtures, said method comprising adding one or more fatty acids having a chain length of C sub 10 to C sub 31, their glycerol esters or both or at least one saturated long chain fatty alcohol, or at least one dicarboxylic acid, or at least one sterol or mixtures thereof at a concentration of 0 1 to 40% with the said liquid neutral organic compounds or their mixtures

The preferred fatty acids employed in the present invention can be selected from decanoic acid, hendecanoic acid, aminohendecanoic acid, dodecanoic acid, aminododecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, heneicosanoic acid docosanoic acid, tπcosanoic acid, tetracosanoic acid, pentacosanoic acid, hexacosanoic acid, heptacosanoic acid, octacosanoic acid, nonacosanoic acid, tπacontanoic acid and hentπacontanoic acid The preferred esters of this invention can be selected from tπlauπn, tπmyπstin, tπpalmitin, tπsteaπn and tπbehenin and mixtures thereof

The preferred liquid neutral organic compounds used in the present invention can be selected from vegetable oils such as coconut oil, groundnut oil, olive oil, palm oil, mustard oil, sunflower oil, neem oil, cottonseed oil, rapeseed oil, soybean oil, sesame oil, corn oil, castor oil, safflower oil, rice bran oil, linseed oil, corn oil, poppy oil, fish oil, tall oil and tung oil, essential oils such as mint oil, camphor oil, cinnamon oils, citrus oil, lemon oil, orange oil, Cyprus oil, eucalyptus oil, geranium oil, jasmine oil, lavender oil, lemon grass oil, rose oil, sandalwood oil, turpentine oil, clove oil, pepper oil and cardamom oil mineral oils such as crude fossil oil, petroleum, diesel and kerosene, and neutral organic solvents such as mono-, di- or tπ-hydπc alcohols, acetone, acetonitπle, aniline, benzene butanol, n-butyl acetate, carbon disulfide, cyclohexane, diethyl ether N,N- dimefhylformamide, dimethyl sulfoxide, 1,4-dιoxan, ethanol, ethyl acetate, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monomethylether, ethyl methyl ketone, methanol, I-propanol, pyπdine, toluene and xylene In a preferred embodiment, the process comprises taking a required part of the fatty acids or their glycerol esters or at least one saturated long chain fatty alcohol, or at least one dicarboxylic acid, or at least one sterol or mixtures thereof in an appropriate vessel with a required part of the desired liquid neutral organic compound followed by heating the mixture and mixing both the liquids thoroughly. The mixture is gradually allowed to solidify at ambient temperature or allowed to cool and solidify at a temperature in the range of 2 deg. C to 10 deg.C or allowed to cool down at a controlled rate of 0.1 deg. C to 1 deg. C per minute to enhance thermal stability.

In another embodiment, the process comprises taking a required part of the fatty acids or their glycerol esters or at least one saturated long chain fatty alcohol, or at least one dicarboxylic acid, or at least one sterol or mixtures thereof in an appropriate vessel and heating the substance till it melts and adding such molten agent with a required part of the desired liquid neutral organic compound followed by heating the mixture and mixing both the liquids thoroughly. The mixture is gradually allowed to solidify at ambient temperature or allowed to cool and solidify at a temperature in the range of 2 deg. C to 10 deg. C or allowed to cool down at a controlled rate of 0.1 deg. C to 1 deg. C per minute to enhance thermal stability.

Preferably, the invention describes a novel process of altering the physical properties such as melting and freezing points of edible oils, non edible oils, essential oils, mineral oils and organic solvents in a temperature dependent manner using fatty acids of chain length C sub. 10 to C sub. 31 and/or saturated fatty acids esters of glycerol or both or at least one saturated long chain fatty alcohol, or at least one dicarboxylic acid, or at least one sterol or mixtures thereof. One of the many advantages of this process is that it does not alter the chemical nature of the above mentioned compounds. Using this invention, the conversion of vegetable oils into higher quality vegetable fats in terms of palatability without chemical hydrogenation and the attendant trace metal contamination was achieved. With this invention, essential oils, mineral oils and organic solvents can be solidified at ambient temperatures, which have several industrial applications The solidified oils can be used in food and feed, dairy and dairy products, cosmetics, healthcare, paints and dyes, lubricants petrochemical and refining, fuels, organic solvents, waxes, storing and transportation laboratory applications, environmental protection, and several other industries

Yet another embodiment of the invention relates to a method of solidifying oils using lipids as activators/catalysts which can find application in the manufacture of vegetable butter, margarine, ghee substitute, chocolate preparation, confectioneries, shoe polish, cosmetic lotions, lubricants, etc It relates to a simple and economical method of obtaining solid fat without chemical hydrogenation, having physical properties that are close to those of chemically hydrogenated products Physical properties of the lipid catalyst derived solid fats are analyzed by melting point apparatus with different percentage of lipids and the melting points of the solids so prepared were determined One of the many advantages of the invention is that it provides a substitute process for chemical hydrogenation Hydrogenation is a process of converting unsaturated fatty acids in liquid oils to a saturated form which in turn converts liquid oil into a solid fat useful in margarine preparation and shortening applications The hydrogenation is an expensive process, creates undesirable trans-fatty acids, and may contain traces of metal contamination The cost and other factors associated with chemical hydrogenation can be avoided if the vegetable oil is converted to solid fat using the lipid catalvst To become a substitute of natural butter and chemically hvdrogenated products, it must fulfill several requirements in the first instance, its cost price should be lower than that of existing products and therefore, its method of manufacturing must be relatively simple Secondly, the physical properties of the substitute must be comparable with other related products Thirdly the chemical composition of the solidified oils must be as close as possible to that of other related products or superior to the existing products It has also been established in this invention that the chemical properties of the solidified oils remain the same such as iodine value, saponification index and fatty acid, and glyceπde contents The prepared solidified oil having low saturated fatty acids and no trans fatty acids is far superior over the hydrogenated fats and natural fats. The prepared solidified oils are especially desirable for human consumption. Common additives such as stabilizer, flavoring agent, emulsifier, anti-spattering agent, colorant, antioxidant, etc. can be added to the solidified oils of the present invention. The applicants observed that when the organic liquid is not neutral then such organic liquid does not solidify by the present method, which establishes that the present invention is restricted to solidification of uncharged liquid/solvents.

According to the present invention, the solid oils are obtained by a simple process of mixing two raw materials and the mixture is then used as such without fractionation. The products prepared in this way have physical characteristics, which are advantageous presumably because of the natural rearrangement of the various constituent molecules that were present initially.

Fatty acids (C sub. 10 to C sub. 31) and their derivatives were used as solidifying agents. Each fatty acid or fatty acid derivative was used separately and in mixture with other fatty acids/derivatives to solidify seed oils, essential oils, mineral oils and organic solvent. The minimum quantity (percent, w/w) of solidifying agent required to solidify each class of organic liquid at 25 deg. C was determined. The melting temperature of each solidified fatty acid/organic liquid mixture was determined.

It was observed that the minimum quantity (percent, w/w) of fatty acid required for the solidification of organic liquids of different classes, decreased sharply with increasing chain-length of the solidifying agent from C sub. 10 to C sub. 19 and remained more or less constant thereafter. The melting temperature of the solidified mixture increased with increasing chain length of the fatty acid that was used as solidifying agent.

The presence of an additional carboxylic acid group at the methyl end of decanoic acid (as in sebacic acid) was found to enhance the solidification ability by more than ten-fold over decanoic acid These dicarboxylic acids (C sub 6 to C sub 10) solidified seed oils and essential oils However, they did not solidify mineral oils

The ability of the agent to solidify organic liquids was enhanced by the presence of an additional hydroxyl group in the middle of the fatty acid chain The presence of a hydroxyl group at the α-carbon (adjacent to carbonyl carbon) in C sub 18 fatty acid was found to adversely affect the ability to solidify seed oils, as compared to stearic acid The additional hydroxyl group in the middle of the chain was observed to play a synergistic role

It was observed that methyl esters of hydroxysteaπc acids had greatly diminished solidifying abilities even though there was an intact hydroxyl group in the middle of the chain Thus, the carbonyl hydroxyl group of the fatty acid is found to play an important role in solidification of organic liquids

The solidifying ability of 12-hydroxystearyl alcohol was found to be nearly identical to that of 12-hydroxysteaπc acid (12-hydroxyoctadecanoιc acid) and many fold higher than that of stearic acid Thus, it may be proposed that two hydroxyl groups, one at the middle and the other at the end of the fatty acid chain are important factors controlling the ability of fatty acids/derivatives to solidify neutral organic liquids

Dihydroxysteaπc acids with the hydroxyl groups adjacent to each other in 'threo or 'erythro' conformation in the middle of the fatty acid chain also solidified all classes of organic liquids studied, but the same compounds showed decreased solidification ability as compared to steaπc acid or 12-hydroxysteaπc acid Thus, more than one hydroxyl group in the middle of the fatty acid chain was found to adversely affect the solidification ability

The presence of an α-hydroxyl group (adjacent to the carbonyl carbon) in C sub 20 and C sub 22 fatty acids was found to decrease the ability of these fatty acids to solidify organic liquids The substitution of hydrogen in the carbonyl hydroxyl with chloride decreased by five-fold, the ability of C sub 22 fatty acid to solidify organic liquid. Thus, the carbonyl hydroxyl of the fatty acid is observed to be an important factor in the solidification of organic liquids. Since the fatty alcohol does not possess a carbonyl group, which was found to solidify all organic liquids at minimal percentages (w/w), it appears that the carbonyl (C=O) group does not appear to be very important for solidification. In the case of C sub. 26 and C sub. 30 fatty acids, the replacement of hydrogen in carbonyl hydroxyl with a methyl group did not decrease the solidifying ability as compared to C sub. 26 and C sub. 30 fatty acids, suggesting that, in addition to carbonyl hydroxyl, the length of carbon chain also plays an important role in solidification.

However, it was observed that there was no significant increase in the solidification ability with very long carbon chains in the absence of a hydroxyl group as in the case of long- chain fatty acyl esters. Thus, carbonyl hydroxyl and carbon chain-length of fatty acids/derivatives were found to be important factors for solidification of organic liquids.

Fatty acids and their derivatives were mixed in equal ratios by weight and used to solidify organic liquids. It was observed that there was no synergistic effect due to the mixing of the solidifying agents.

The ability of stearic acid (solid at room temperature) to solidify fatty acids that are liquid at room temperature was studied. It was observed that the minimum quantity of stearic acid required to solidify liquid fatty acids like ethanoic acid, propanoic acid, butanoic acid, hexanoic acid, heptanoic acid, octanoic acid and nonanoic acid (C sub. 2 to C sub. 9) increased with the chain-length of the liquid fatty acid.

The rate of evaporation of volatile mineral oils and solvents was found to decrease after solidification. The rate of evaporation was inversely proportional to the chain length of the fatty acid used for solidification. Apart from fatty acids, it was observed that cholesterol, cholic acid and deoxycholic acid can also solidify seed oil in amounts comparable to long-chain saturated fatty acids

However, cholesteryl oleate did not solidify seed oil even at four-fold higher concentrations

The mechanism of the present invention may be thought of as a) the fatty acids by virtue of having hydrophobic and a charged hydrophilic components align themselves in a head to tail linear and perhaps perpendicular fashion to create a lattice structure with sufficient spacing for the other liquid neutral organic compounds embedded in the lattice to form a gel to solid structure. b) alternatively, they could also form a large spherical monolayer entrapping the neutral organic compounds in the interior hydrophobic environment thus, leading to the change of liquid to solid physical form.

EXAMPLES

The following examples are provided by way of illustrations only and these should not be construed to limit the scope of the invention in any manner

Example 1

One hundred grams of the solid kokum oil was dissolved in 200 ml of n-hexane and loaded onto a silica gel (200 g) column (pre-equilibrated with hexane) and washed the column with 2 liters of n-hexane The n-hexane was removed from the eluted fraction by evaporation under vacuum. Specific amounts of kokum fat were mixed with the indicated amounts of sunflower oil. The tubes were heated to melt the kokum fat, and were mixed thoroughly Then the tubes were kept at the various temperatures indicated Table 2b summarizes the effect of the isolated kokum fat on the solidification of sunflower oil

Table 2b. Solidification of sunflower oil with various concentrations of kokum fat

^■+^' indicates solidification. ^"-^" indicates no solidification

Example 2

Glycerol esters of C sub 12, C sub. 14, C sub 16 and C sub 18 fatty acids (trilaurin, trimyristin, tripalmitin, and tristearin) and hydrogenated vegetable oils were used as solidifying agents to solidify liquid oils. The above-mentioned agent was mixed at 20-40 percent of total weight with various quantities of liquid oils selected from the group comprising of edible, non-edible liquid oils, and essential oils The mixture was heated to melt the agent and was allowed to solidify at 4 deg. C. The results are summarized in Table

Table 3. Percentage of Glycerol Esters of Fatty Acid Used to Solidify Liquid Oils

S No Solidifying Agent Percentage Used

1 Trilaurin 35

2 Trimyristin 30

Tripalmitin 25

4 Tristearin 20

5 Hydrogenated Sunflower Oil 20

6 Hydrogenated Castor Oil 20

Example 3 Various commercially available fatty acids were tested for solidification ability and the results of such experiments are given in the following examples which are provided by way of illustration and not by limitation. Saturated fatty acids from C sub 10 to C sub 31 were tested for their ability to solidify various organic liquids like sunflower oil, lavender oil, diesel, petrol, kerosene and acetone. Fatty acids of varying chain-lengths were mixed with the indicated amounts of oil/solvent. The tubes were heated to melt the saturated fatty acids and were kept at 25 deg C for solidification. The melting temperatures of the solidified mixtures were determined and the results are summarized in Tables 4 and 5

Table 4. Minimum Percent of Fatty Acid Required for Solidification of Organic Liquids and Melting Point (MP) of the Solidified Mixture

nd = Not Determined Table 5. Minimum Percent of Fatty Acid Required for Solidification of Organic Liquids and Melting Point (MP) of the Solidified Mixture

S.No Fatty Acid Petrol Kerosene Acetone

Percent MP Percent MP Percent MP (deg. C) (deg. C) (deg. C)

1. Decanoic acid 90 33-37 95 32-37 >95 ND

2_. Dodecanoic acid 60 34-38 60 30-35 70 30-35

—> Tetradecanoic acid 30 31-35 30 35-40 50 30-35

4. Hexadecanoic acid 20 30-33 15 31-38 30 30-35

5- Octadecanoic acid 15 30-33 12 46-52 20 40-45

6. Nonadecanoic acid 8 30-34 6 31-38 6 30-35

7 Eicosanoic acid 8 30-34 6 34-40 6 30-35

8. Heneicosanoic acid 6 39-43 5 36-42 8 40-45

9. Docosanoic acid 5 40-43 4 39-46 8 45-50

10. Tricosanoic acid 5 43-47 4 46-51 5 45-50

11. Tetracosanoic acid 5 44-47 5 47-54 3 40-44

12. Pentacosanoic acid 5 44-48 5 48-55 41 -44

13. Hexacosanoic acid 4 47-51 5 53-60 3 41-45

14. Heptacosanoic acid 5 46-50 5 57-63 nd nd

15. Octacosanoic acid 4 49-53 4 58-65 nd nd

16. Nonacosanoic acid 4 46-50 5 59-66 nd nd

17. Triacontanoic acid 4 55-58 4 61-67 nd nd

18. Hentriacontanoic acid 4 54-58 4 63-70 nd nd nd = Not Determined

Example 4

Modified saturated fatty acids from C sub. 6 to C sub. 30 were tested for their ability to solidify various organic liquids like sunflower oil, lavender oil, diesel, petrol, kerosene and acetone. The modified fatty acids of various chain-lengths were mixed with the indicated amounts of oil/solvent. The tubes were heated to melt the modified saturated fatty acids, mixed thoroughly and kept at 25 deg. C for solidification. The melting temperatures of the solidified mixtures were determined. The results are summarized in Table 6 and 7. Table 6. Minimum Percent of Modified Fatty Acid Required for the Solidification of Organic Liquids and Melting Point (MP) of the Solidified Mixture

S.No Fatty Acid Sunflower Lavender Diesel Percent MP Percent MP Percent MP (deg. C) (deg. C) (deg. C)

1. 1 1-Aminoundecanoic 15 35-40 nd nd nd nd acid

2. 12-Aminododecanoic 40 38-45 nd nd nd nd acid

- J . 2-hydroxyoctadecanoic >4 nd nd nd 6 65-70 acid

4. Methyl-2- >4 nd nd nd >6 nd hydroxyoctadecanoic acid

5. 12-hydroxy1 41-44 2 40-42 1 65-68 octadecanoic acid

6. Methyl- 12-hydroxy10 35-40 >6 nd >6 nd octadecanoic acid

7. 1 , 12-octadecanediol 1 39-42 2 42-45 1 65-70

8. threo-9, 10-dihydroxy- 1 50-55 8 50-55 10 83-88 octadecanoic acid

9. erythro-9,10- 4 81-84 6 97-102 14 120- 125 dihydroxy- octadecanoic acid

10. 1-Eicocosanol 40-45 4 49-52 4 59-62

1 1. 2-hydroxyeicasanoic >4 nd 8 55-58 6 72-75 acid

12. Methyl-2- >4 nd nd nd 6 39-42 hydroxyeicasanoic acid

13. Docosanoic acid 4 30-35 10 35-40 5 40-45 methyl ester

14. 2-hydroxydocosanoic >4 nd nd nd >3 acid 1

15. 1-Docasanol ->

J 43-47 3 50-53 - 42-44 !

16 Behenoyl chloride 10 45-50 12 55-60 nd nd !

17 Hexacosanoic acid- 2 39-42 35-40 5 45-50 ! methyl ester

18. 1-Hexacosanol 3 45-48 2 39-43 2 50-52

19. Triacontanoic acid- -

J 40-43 2 37-40 6 40-45 methyl ester 20. 1-Triacontanol 4 55-60 nd nd 3 62-65

21 Adipic acid 4 140-145 3 89-92 >8 nd

22. Suberic acid 4 80-85 5 77-80 >10 nd

23. Sebacic acid 4 80-85 5 77-80 >10 nd

24. Behenic anhvdride 1 67-70 5 48-53 1 49-53

25. Behenic acid-myristyl 2 35-38 3 59-62 > 5 nd ester

26. Behenic acid-palmityl 2 35-38 3 42-46 > 4 nd ester

27. Behenic acid-stearyl 1 42-45 2 48-51 2 41-43 ester

28. Behenic acid-arachidyl 2 42-45 3 49-52 2 41-43 ester

29. Behenic acid-behenyl 63-66 nd nd > 4 nd ester i nd = Not Determined

Table 7. Minimum Percent of Modified Fatty Acid Required for Solidification of Organic Liquids and Melting Point (MP) of the Solidified Mixture

S.No Fatty Acid Petrol Kerosene Acetone

Percent MP Percent MP Percent MP (deg. C) (deg. C) ( deg. C)

1. 2-hydroxyoctadecanoic 16 34-40 nd nd nd nd acid

2. 12-hydroxy8 58-60 8 42-45 8 40-45 octadecanoic acid

Methyl- 12-hydroxy>15 nd 15 35-37 > 8 nd

³ octadecanoic acid

4. 1 , 12-octadecanediol 8 55-60 8 65-70 7 50-55

5. threo-9, 10-dihydroxy- 20 88-93 24 98-103 15 55-60 octadecanoic acid

6. erythro-9, 10-dihydroxy- 20 97-102 20 105-1 10 15 60-65 octadecanoic acid

7. 1-Eicocosanol 8 49-52 8 49-52 5 40-45

2-hydroxyeicasanoic 8 45-50 10 72-75 10 55-60 ;

8. acid

9 Methyl-2- >12 nd nd nd nd nd hydroxyeicasanoic acid

10. Docosanoic acid methyl >15 nd >15 nd 10 35-40 ester π 1-Docosanol 8 45-50 5 52-56 6 45-50

12. Behenoyl chloride >20 nd >20 nd 20 50-55 13. Hexacosanoic acid- 8 40-45 10 50-55 10 50-55 methvl ester

14. 1-Hexacosanol - j 39-42 45-50 nd nd

15. Triacontanoic acid- 5 35-40 7 45-50 nd nd methyl ester

16. 1-Triacontanol 4 44-49 nd nd nd nd

17. Adipic acid >20 nd >10 nd nd nd

18. Suberic acid >20 nd >10 nd nd nd

19. Sebacic acid >15 nd >12 nd nd nd

20. Behenic anhvdride 8 65-70 10 75-80 nd nd

21. Behenic acid-myristyl >15 nd nd nd nd nd ester

22. Behenic acid-stearyl > 6 nd 5 nd nd nd ester

23. Behenic acid-arachidyl > 7 nd 5 nd nd nd ester

24. Behenic acid-behenyl > 7 nd > 7 nd nd nd ester nd = Not Determined

Example 5

Stearic acid was used as an agent to solidify various organic liquids like solvents, ethanol, methanol, liquid fatty acids, and triolein. Stearic acid was mixed with various amounts of organic liquids and tubes heated to melt the agent. After thorough mixing, the tubes were left at 25 deg. C for solidification. The melting temperatures of the solidified mixtures were determined. The results are summarized in Table 8.

Table 8. Other Organic Liquids Solidified With Fatty Acid

Example 6

Stearic acid was used as the agent to solidify various essential oils Steaπc acid was mixed with various amounts of essential oils and the tubes were heated to melt the agent After thorough mixing, the tubes were left at 25 deg C for solidification The results are summarized in Table 9

Table 9. Essential Oils Solidified With Fatty Acid

Example 7

Sterols like cholesterol and deoxycholic acid and sterol esters like cholesteryl oleate were tested for their ability to solidify sunflower oil Each one of these agents was mixed with various amounts of sunflower oil and the vessels heated to melt the agent Following heating, the contents of the tubes were mixed thoroughly and kept at 25 deg C for solidification The data is summarized in Table 10 Table 10. Solidification Of Sunflower Oil With Other Agents

Example 8

The mixture of fatty acids, modified fatty acids and fatty alcohols, were used in 1 : 1 ratio for solidification of organic liquids. The above-mentioned 1 : 1 mixtures of agents were mixed with the indicated amounts of oil/solvent. The tubes were heated to melt the agents and the contents were mixed thoroughly. The tubes were then kept at 25 deg. C for solidification. The melting temperatures of the solidified mixtures were determined. The data is summarized in Tables 1 la-1 lg.

Mixtures of Two Solidifying Agents

Table 11a. Stearic acid + 12-hydroxy-stearic acid

Sunflower Lavender Diesel Percent MP Percent MP Percent MP

>2 nd >4 nd 3 45-50°C

Table lib. Stearic acid + 12-hydroxy-stearyl alcohol

Sunflower Lavender Diesel Petrol I Kerosene Percent MP Percent MP Percent MP Percent MP i Percent MP

>2 nd >4 nd 45-50°C 15 45-50°C 12 45-50°C

Table lie. threo-9,10-Dihydroxy-stearic acid + Adipic Acid

Sunflower Lavender Percent MP Percent MP

75-80°C 8 100-105°C

Table lid. Behenic acid + Behenyl-alcohol

Sunflower Lavender Diesel Petrol Percent MP Percent MP Percent MP Percent MP

35-40°C >3 nd 40-45°C 40-45°C

Table lie. Behenic acid + Behenic-anhydride

Sunflower Lavender Diesel Petrol Percent MP Percent MP Percent MP Percent MP

45-50°C 50-55°C 55-60°C 12 45-50°C

Kerosene Acetone Percent MP Percent MP

8 45-50°C 40-45°C

Table llf. Behenyl-alcohol + Adipic Acid

Sunflower Lavender Percent MP Percent MP

70-75°C >3 nd

Table llg. Hexacosanoic acid + Hexacosanol

Sunflower Lavender Diesel Petrol Percent MP Percent MP Percent MP Percent MP

40-45°C 45-50°C 45-50°C 40-45°C

1 1 (w/w) mixture used at the indicated total percentage nd = Not Determined

MP = Meltins; Point of the solid Example 9

Mixtures of four solidifying agents showing the best solidification properties were used in equal ratio (1 1 1 1) mixtures for solidifying organic liquids The solidifying agents were mixed with various organic liquids and the tubes heated to melt the agents The contents of the tubes were mixed thoroughly and the tubes kept at 25 deg C for solidification The melting temperatures of the solids were determined The data is summarized in Tables 12a and 12b

Mixtures of Four Solidifying Agents

Table 12a. Stearic acid + 12-hydroxy-stearyl-alcohol + Behenic acid + Behenyl- alcohol

Sunflower Lavender Diesel Petrol Percent MP Percent MP Percent MP Percent MP

35-40°C 35-40°C 40-45°C 13 40-45°C

Kerosene Acetone Percent MP Percent MP

10 55-60°C 40-45°C

Table 12b. Stearic acid + threo-9,10-dihydroxy-stearic acid + Behenic acid + Behenic- anhydride

Sunflower Lavender Diesel Petrol Kerosene Percent MP Percent MP Percent MP Percent MP Percent MP

3 43-47°C 7 45-50°C 65-70°C 16 65-70°C 19 80-85°C

1 1 1 1 (by weight) mixture of four fatty acids used at the indicated total percentage nd = Not Determined

MP = Melting Point of the solid Example 10

The change in rates of evaporation o volatile organic liquids like mineral oils and solvents after solidification was studied 7 he volatile organic liquids were mixed with appropriate amounts of solidifying agent (stearic acid or behenic acid) and the tubes were heated to melt the agent The contents of the tubes were mixed thoroughly and the tubes were kept at 25 deg C for solidification The solidified liquids were incubated at 25 deg C for 12 h and the respective decreases in weight were recorded and compared with the appropriate controls The results are summarized in Tables 13 and 14

Table 13. Rate of Evaporation of Solidified Volatile Organic Liquids

Solidified With Steaπc or Behenic acids Control

Organic Percent Percent Percent Percent Percent Liquid C18 0 Drop in C22 0 Drop in Drop in Weight Weight Weight

Diesel 4 0 45 3 0 00 Only Diesel 1 10

Petrol 15 6 60 6 10 00 Only Petrol 15 00

Kerosene 12 1 10 2 0 76 Only Kerosene 1 70

Acetone 10 86 00 2 67 0 Only Acetone 86 00

Table 14. Decrease in Evaporation Rate After Solidification

Example 11

Methods of solidifying sunflower oil are given in the Example 1 1

a) Five grams of stearic acid were taken in a 250-ml beaker and heated to melt the said fatty acid To the melted fatty acid, 95 grams of commercially available sunflower oil was added and mixed by stirring The mixture was heated up to 70 deg C and mixture cooled at 4 deg C for 15 minutes After cooling, the mixture was incubated at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

b) Four grams of behenic acid were taken in a 250-ml beaker and heated to melt the said fatty acid To the melted fatty acid, 95 grams of commercially available sunflower oil was added and mixed by stirring The mixture was heated up to 80 deg C and the mixture cooled at 4 deg C for 15 minutes After cooling, the mixture was incubated at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

c) Five grams of steaπc acid were taken in a 250-ml beaker and heated to melt the said fatty acid To the melted fatty acid, 95 grams of sunflower oil was added and mixed by stirring The mixture was heated up to 70 deg C and the mixture cooled and incubated at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

d) Four grams of behenic acid was taken in a 250-ml beaker and heated to melt the said fatty acid To the melted fatty acid, 95 grams of commercially available sunflower oil was added and mixed by stirring The mixture was heated up to 80 deg C The mixture was cooled and kept at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

The results are summarized in Table 15 Example 12

Methods of solidifying mustard oil are given in Example 12

a) Five grams of stearic acid were taken in a 250-ml beaker and heated to melt the said fatty acid To the melted fatty acid, 95 gram of mustard oil was added and mixed by stirring. The mixture was heated up to 70 deg C and mixture cooled at 4 deg C for 15 minutes After cooling, the mixture was incubated at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

b) Five grams of behenic acid were taken in a 250-ml beaker and heated to melt the said fatty acid To the melted fatty acid, 95 grams of mustard oil was added and mixed by stirring. The mixture was heated up to 80 deg. C and mixture cooled at 4 deg C for 15 minutes After cooling, the mixture was incubated at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined.

c) Five grams of stearic acid were taken in a 250-ml beaker and heated to melt the said fatty acid To the melted fatty acid, 95 grams of mustard oil was mixed by stirring The mixture was heated up to 70 deg C and the mixture incubated at 26 to 28 deg C The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

d) Four grams of behenic acid were taken in a 250-ml beaker and heated to melt the said fatty acid To the melted fatty acid, 95 grams of commercially available mustard oil was added and mixed by stirring The mixture was heated up to 80 deg C The mixture was incubated at 26 to 28 deg C The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

The results are summarized in Table 15

Example 13

Methods of solidifying Groundnut oil are given in Example 13

a) Five grams of stearic acid were taken in a 250-ml beaker and heated to melt the said fatty acid To the melted fatty acid, 95 grams of groundnut oil was mixed by stirring The mixture was heated up to 70 deg C and mixture cooled at 4 deg C for 15 minutes After cooling, the mixture was incubated at 26 to 28 deg C The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

b) Five grams of behenic acid were taken in a 250-ml beaker and heated to melt the said fatty acid To the melted fatty acid, 95 grams of groundnut oil was added and mixed by stirring The mixture was heated up to 80 deg C and mixture cooled at 4 deg C After cooling, the mixture was incubated at 26 to 28 deg C The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

c) Five grams of stearic acid were taken in a 250-ml beaker and heated to melt the said fatty acid To the melted fatty acid, 95 grams of groundnut oil was added and mixed by stirring The mixture was heated up to 70 deg C and the mixture incubated at 26 to 28 deg C The solidified product remained solid at ambient temperature The melting temperature of the solid was determined d) Four grams of behenic acid were taken in a 250-ml beaker and heated to melt the said fatty acid. To the melted fatty acid, 95 grams of commercially available groundnut oil was added and mixed by stirring. The mixture was heated up to 80 deg. C. The mixture was incubated at 26 to 28 deg. C. The solidified product remained solid at ambient temperature. The melting temperature of the solid was determined.

The results are summarized in Table 15.

Example 14

Methods of solidifying castor oil are given in Example 14.

a) Five grams of stearic acid were taken in a 250-ml beaker and heated to melt the said fatty acid. To the melted fatty acid, 95 grams of castor oil was added and mixed by stirring. The mixture was heated up to 70 deg. C and mixture cooled at 4 deg. C. After cooling, the mixture was incubated at 26 to 28 deg. C. The solidified product remained solid at ambient temperature. The melting temperature of the solid was determined.

b) Five grams of behenic acid were taken in a 250-ml beaker and heated to melt the said fatty acid. To the melted fatty acid, 95 grams of castor oil was added and mixed by stirring. The mixture was heated up to 80 deg. C and mixture cooled at 4 deg. C. After cooling, the mixture was incubated at 26 to 28 deg. C. The solidified product remained solid at ambient temperature. The melting temperature of the solid was determined.

c) Five grams of stearic acid was taken in a 250-ml beaker and heated to melt the said fatty acid. To the melted fatty acid, 95 grams of castor oil was added and mixed by stirring. The mixture was heated up to 70 deg. C and the mixture incubated at 26 to 28 deg C. The solidified product remained solid at ambient temperature The melting temperature of the solid was determined.

d) Four grams of behenic acid was taken in a 250-ml beaker and heated to melt the said fatty acid To the melted fatty acid, 95 grams of commercially available castor oil was added and mixed by stirring. The mixture was heated up to 80 deg C The mixture was kept at 26 to 28 deg. C The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

The results are summarized in Table 15

Example 15

Methods of solidifying geraniol are given in Example 15

a) Five grams of stearic acid were taken in a 250-ml beaker and heated to melt the said fatty acid. To the melted fatty acid, 95 grams of commercially available geraniol were added and mixed by stirring. The mixture was heated up to 70 deg C and mixture cooled at 4 deg. C for 15 minutes After cooling, the mixture was incubated at 26 to 28 deg. C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

b) Four grams of behenic acid were taken in a 250-ml beaker and heated to melt the said fatty acid To the melted fatty acid, 95 grams of commercially available geraniol was added and mixed by stirring The mixture was heated up to 80 deg C and the mixture cooled at 4 deg C for 15 minutes After cooling, the mixture was incubated at 26 to 28 deg. C for about 2 hours The solidified product remained solid at ambient temperature. The melting temperature of the solid was determined c) Five grams of stearic acid were taken m a 250-ml beaker and heated to melt the said fatty acid To the melted fatty acid, 95 grams of commercially available geraniol were added and mixed by stirring The mixture was heated up to 70 deg C and the mixture was incubated at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

d) Four grams of behenic acid were taken in a 250-ml beaker and heated to melt the said fatty acid To the melted fatty acid, 95 grams of commercially available geraniol was added and mixed by stirring The mixture was heated up to 80 deg C and the mixture was incubated at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

The results are summarized in Table 15

Example 16

Methods of solidifying citral are given in Example 16

a) Five grams of steaπc acid were taken in a 250-ml beaker and heated to melt the said fatty acid To the melted fatty acid, 95 grams of commercially available citral were added and mixed by stirring The mixture was heated up to 70 deg C and mixture cooled at 4 deg C for 15 minutes After cooling, the mixture was incubated at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

b) Four grams of behenic acid were taken in a 250-ml beaker and heated to melt the said fatty acid To the melted fatty acid, 95 grams of commercially available citral was added and mixed by stirring The mixture was heated up to 80 deg C and the mixture cooled at 4 deg C for 15 minutes After cooling, the mixture was incubated at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

c) Five grams of stearic acid were taken in a 250-ml beaker and heated to melt the said fatty acid To the melted fatty acid, 95 grams of commercially available citral were added and mixed by stirring The mixture was heated up to 70 deg C and the mixture was incubated at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

d) Four grams of behenic acid were taken in a 250-ml beaker and heated to melt the said fatty acid To the melted fatty acid, 95 grams of commercially available citral was added and mixed by stirring The mixture was heated up to 80 deg C and the mixture was incubated at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

The results are summarized in Table 15

Example 17

Methods of solidifying diesel are given in Example 17

a) Five grams of stearic acid were taken in a 250-ml beaker and heated at 70 deg C to melt the said fatty acid To the melted fatty acid, 95 grams of commercially available diesel was added and mixed by stirring The mixture was heated up to 50 deg C and mixture cooled at 4 deg C for 15 minutes After cooling, the mixture was incubated at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined b) Four grams of behenic acid were taken in a 250-ml beaker and heated at 80 deg C to melt the said fatty acid To the melted fatty acid, 95 grams of commercially available diesel was added and mixed by stirring The mixture was heated up to 50 deg C and the mixture cooled at 4 deg C for 15 minutes After cooling, the mixture was incubated at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

c) Five grams of stearic acid were taken in a 250-ml beaker and heated at 70 deg C to melt the said fatty acid To the melted fatty acid, 95 grams of diesel was added and mixed by stirring The mixture was heated up to 50 deg C and the mixture cooled and incubated at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

d) Four grams of behenic acid was taken in a 250-ml beaker and heated at 80 deg C to melt the said fatty acid To the melted fatty acid, 95 grams of commercially available diesel was added and mixed by stirring The mixture was heated up to 50 deg C The mixture was cooled and kept at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

The results are summarized in Table 15

Example 18

Methods of solidifying kerosene are given in Example 18

a) Five grams of stearic acid were taken in a 250-ml beaker and heated at 70 deg C to melt the said fatty acid To the melted fatty acid, 95 grams of commercially available kerosene was added and mixed by stirring The mixture was heated up to 50 deg C and mixture cooled at 4 deg C for 15 minutes After cooling, the mixture was incubated at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

b) Four grams of behenic acid were taken in a 250-ml beaker and heated at 80 deg C to melt the said fatty acid To the melted fatty acid, 95 grams of commercially available kerosene was added and mixed by stirring The mixture was heated up to 50 deg C and the mixture cooled at 4 deg C for 15 minutes After cooling, the mixture was incubated at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

c) Five grams of stearic acid were taken in a 250-ml beaker and heated at 70 deg C to melt the said fatty acid To the melted fatty acid, 95 grams of kerosene was added and mixed by stirring The mixture was heated up to 50 deg C and the mixture cooled and incubated at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

d) Four grams of behenic acid was taken in a 250-ml beaker and heated at 80 deg C to melt the said fatty acid To the melted fatty acid, 95 grams of commercially available kerosene was added and mixed by stirring The mixture was heated up to 50 deg C The mixture was cooled and kept at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

The results are summarized in Table 15 Example 19

Methods of solidifying acetone are given in Example 19

a) Five grams of stearic acid were taken in a 250-ml beaker and heated at 70 deg C to melt the said fatty acid. To the melted fatty acid, 95 grams of commercially available acetone was added and mixed by stirring. The mixture was heated up to 40 deg C and mixture cooled at 4 deg. C for 15 minutes After cooling, the mixture was incubated at 26 to 28 deg. C. for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

b) Four grams of behenic acid were taken in a 250-ml beaker and heated at 80 deg. C to melt the said fatty acid. To the melted fatty acid, 95 grams of commercially available acetone was added and mixed by stirring. The mixture was heated up to 40 deg C and the mixture cooled at 4 deg. C for 15 minutes After cooling, the mixture was incubated at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined.

c) Five grams of stearic acid were taken in a 250-ml beaker and heated at 70 deg. C to melt the said fatty acid To the melted fatty acid, 95 grams of acetone were added and mixed by stirring The mixture was heated up to 40 deg C and the mixture cooled and incubated at 26 to 28 deg C for about 2 hours. The solidified product remained solid at ambient temperature. The melting temperature of the solid was determined d) Four grams of behenic acid was taken in a 250-ml beaker and heated at 80 deg C to melt the said fatty acid To the melted fatty acid, 95 grams of commercially available acetone was added and mixed by stirring The mixture was heated up to 40 deg C The mixture was cooled and kept at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

The results are summarized in Table 15

Example 20

Methods of solidifying methanol/alcohol are given in Example 20

a) Five grams of stearic acid were taken in a 250-ml beaker and heated at 70 deg C to melt the said fatty acid. To the melted fatty acid, 95 grams of commercially available methanol was added and mixed by stirring The mixture was heated up to 40 deg C and mixture cooled at 4 deg. C for 15 minutes After cooling, the mixture was incubated at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

b) Four grams of behenic acid were taken in a 250-ml beaker and heated at SO deg C to melt the said fatty acid To the melted fatty acid, 95 grams of commercially available methanol was added and mixed by stirring The mixture was heated up to 40 deg C and the mixture cooled at 4 deg C for 15 minutes After cooling, the mixture was incubated at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined c) Five grams of stearic ac d were taken in a 250-ml beaker and heated at 70 deg C to melt the said fatty acid To the melted fatty acid, 95 grams of alcohol were added and mixed by stirring The mixture was heated up to 40 deg C and the mixture cooled and incubated at 26 to 28 deg. C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

d) Four grams of behenic acid was taken in a 250-ml beaker and heated at 80 deg C to melt the said fatty acid To the melted fatty acid, 95 grams of commercially available alcohol was added and mixed by stirring The mixture was heated up to 40 deg C The mixture was cooled and kept at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

The results are summarized in Table 15

Example 21

Methods of solidifying dimethyl sulfoxide are given in Example 21

a) Five grams of stearic acid were taken in a 250-ml beaker and heated at 70 deg C to melt the said fatty acid To the melted fatty acid, 95 grams of commercially available dimethyl sulfoxide was added and mixed by stirring The mixture was heated up to 40 deg C and mixture cooled at 4 deg C for 15 minutes After cooling, the mixture was incubated at 26 to 28 deg C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined

b) Four grams of behenic acid were taken in a 250-ml beaker and heated at 80 deg C to melt the said fatty acid To the melted fatty acid, 95 grams of commercially available dimethyl sulfoxide was added and mixed by stirring. The mixture was heated up to 40 deg. C and the mixture cooled at 4 deg. C for 15 minutes After cooling, the mixture was incubated at 26 to 28 deg. C for about 2 hours The solidified product remained solid at ambient temperature. The melting temperature of the solid was determined

c) Five grams of stearic acid were taken in a 250-ml beaker and heated at 70 deg C to melt the said fatty acid. To the melted fatty acid, 95 grams of dimethyl sulfoxide were added and mixed by stirring. The mixture was heated up to 40 deg C and the mixture cooled and incubated at 26 to 28 deg. C for about 2 hours The solidified product remained solid at ambient temperature The melting temperature of the solid was determined.

d) Four grams of behenic acid was taken in a 250-ml beaker and heated at 80 deg. C to melt the said fatty acid. To the melted fatty acid, 95 grams of commercially available dimethyl sulfoxide was added and mixed by stirring The mixture was heated up to 40 deg C The mixture was cooled and kept at 26 to 28 deg. C for about 2 hours. The solidified product remained solid at ambient temperature The melting temperature of the solid was determined.

The results are summarized in Table 15

Table 15. Solidification of Organic Liquids with Stearic or Behenic acids

¹ ! Melting Point ' ι Melting Point

Example j Percent | Rapid Slow { Percent Rapid Slow

Organic , Stearic Cooled Cooled ' Behenic Cooled Cooled

Liquid Acid (deg. C) (deg. C) ^! Acid (deg. C) (deg. C)

Sunflower 5 38-42 41 -46 4 51-57 53-57

Mustard 5 37-40 38-44 4 50-54 51 -57 ^'

Groundnut 5 37-44 42-45 4 50-55 49-55 !

Castor ; 5 34-39 38-42 , 4 47-51 46-51 Geraniol 5 30-34 33-38 i 4 31-35 39-47

Citral 5 33-40 36-42 ! 4 37-43 41-48

Diesel 5 32-37 32-39 ^■ 4 44-47 47-53

Kerosene 12 42-47 46-52 ⁱ 8 41-45 43-47

Acetone 20 38-43 40-44 ^■ 8 43-48 45-50

Methanol 10 38-44 40-45 , 8 53-57 54-58

Dimethyl 7 33-39 35-40 | 8 53-56 55-57 Sulfoxide

Rapid Cooled = The melt was kept at 4 deg. C for solidification; Slow Cooled = The melt was kept at 25 deg. C for solidification.

Liquefaction of the solid/semi-solid preparation made by the addition of free fatty acids

The method of liquefaction of the solid/semi-solid preparations consisted of taking 100 grams of the solid, melting it to the state of liquid. To the melted mixture, 17 grams of sodium hydroxide (17 percent weight/weight aqueous sodium hydride solution) was added and stirred for 10 minutes. After alkali treatment, the mixture was filtered. To the filtrate equal amount of hot water was added, stirred and allowed to settle. The aqueous layer was removed and the process was repeated again. The moisture in the oil was removed under reduced pressure.

Recovery of added fatty acid

The free fatty acid added in the original preparation was removed by the alkaline treatment as described above. Fifty milliliters of concentrated hydrochloric acid (12 N) was added until the pH became acidic and the free fatty acid was separated by filtration. Alternatively, the added fatty acids or their glycerol esters were recovered by fractional distillation.

Recovery of added other solidifying agent

The added solidifying agent was recovered by conventional fractional distillation process. Example 22

Liquefaction of the solid/semi-sohd preparation made by the addition of free fatty acids

The method of liquefaction of the solid/semi-sohd preparations consisted of taking 100 grams of the solidified mixture, melting it to the state of liquid To the melted mixture 17 grams of sodium hydroxide (17 percent weight/weight aqueous sodium hydroxide solution) was added and stirred for 10 minutes After alkali treatment, the mixture was filtered to remove the salts of fatty acids The filtrate (starting commodity) was recovered

Excess or unreacted sodium hydroxide in the filtrate was removed by the addition of equal amount of hot water stirred and allowed to settle The aqueous layer was removed and discarded The moisture in the oil was removed under reduced pressure

In an another method, the solidified oil or solidified organic solvent was melted to liquefy the solid

Example 23

Recovery of added fatty acid

The free fatty acid added for solidification was removed by the alkaline treatment as described in Example 22 Fifty milliliters of concentrated hydrochloric acid (12 N) was added until the pH became acidic and the free fatty acid was separated by filtration

Alternatively, the added fatty acids or their glycerol esters were recovered bv fractional distillation

Example 24

Recovery of added other

One hundred gram of solidified solid/semi-sohd preparations was melted to liquid state and distilled the mixture to separate the added solidifying agent The solidified commoditv was recovered also bv conventional fractional distillation process

Claims

1 A novel synergistic solid /semi-solid organic composition, comprising

a) at least one saturated long chain fatty acid and/or its glycerol esters, or at least one saturated long chain fatty alcohols, or at least one dicarboxylic acid, or at least one sterol or mixtures thereof and b) one or more liquid neutral organic compounds, said ingredients (a) being present in a ratio between 0 1 to 40 percent by weight and the remaining part from (b)

2 A composition as claimed in claim 1 wherein the fatty acid has a chain length from C sub lO to C sub 31

3 A composition as claimed in claim 1 wherein the said fatty acid can be selected from decanoic acid, hendecanoic acid, aminohendecanoic acid, dodecanoic acid, aminododecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, heneicosanoic acid, docosanoic acid, tπcosanoic acid, tetracosanoic acid, pentacosanoic acid, hexacosanoic acid, heptacosanoic acid, octacosanoic acid, nonacosanoic acid, tπacontanoic acid and hentπacontanoic acid

4 A composition as claimed in claim 1 wherein the glycerol esters can be selected from trilaurin, trimyristin, tripalmitin, tristearin and tπbehenin or mixtures thereof

5 A composition as claimed in claim 1 wherein the saturated long-chain fatty alcohols can be selected from C sub 18 to C sub 30 fatty alcohols A composition as claimed in claim 1 wherein the dicarboxylic acids can be selected from C sub 6 to C sub 10 dicarboxylic acids

A composition as claimed in claim 1 wherein the sterol can be selected from cholesterol or deoxycholic or cholic acid

A composition as claimed in claim 1 wherein the saturated long chain hydroxvlated fatty acids can be selected from C sub 16 to C sub 30

A composition as claimed in claim 1 wherein the said liquid neutral organic compound can be selected from vegetable oils, essential oils, mineral oils and neutral organic solvents

A composition as claimed in claim 1 wherein when the saturated long chain hydroxylated fatty acid is used, the said liquid neutral organic compound can be selected from essential oils and neutral organic solvents

A composition as claimed in claim 9 wherein the said vegetable oil can be selected from coconut oil, groundnut oil, olive oil, palm oil, mustard oil, sunflower oil, nee oil, cottonseed oil, rapeseed oil, soybean oil, sesame oil, corn oil, castor oil, safflower oil, rice bran oil, linseed oil, corn oil, poppy oil, fish oil, till oil and tung oil

A composition as claimed in claim 9 wherein the said essential oils can be selected from mint oil, camphor oil, cinnamon oils, citrus oil, lemon oil, orange oil, Cyprus oil, eucalyptus oil, geranium oil, jasmine oil, lavender oil, lemon grass oil, linolae oil, rose oil, sandalwood oil, turpentine oil, clove oil, pepper oil and cardamom oil A composition as claimed in claim 9 wherein the said mineral oils are selected from crude fossil oil, petroleum, diesel and kerosene

A composition as claimed in claim 9 wherein the said neutral organic solvents are selected from mono-, di-, or tπ-hydπc alcohols, acetone, acetonitπle, aniline benzene, 1-butanol, 2-butanol, tert-butanol, iso-butanol, n-butyl acetate, carbon disulfide, cyclohexane, diethyl ether, N,N-dιmefhylformamιde, dimethyl sulfoxide

1 4-dιoxan, ethanol, ethylacetate, ethylene glycol, ethylene glycol monoethyl ether ethylene glycol monomethylether, ethyl methyl ketone, methanol, I-propanol, pyπdine, toluene and xylene

A composition as claimed in claims 1, 1 1, 12, 13 and 14 wherein 10% by Wt of kokum fat is required to solidify sunflower oil, 15% by Wt of kokum fat is required to solidify lavender oil, 20% by Wt is required to solidify petrol, 20% by Wt is required to solidify kerosene and 20% by Wt is required to solidify acetone

A process for producing a novel synergistic solid/semi-sohd organic composition said process comprising mixing (a) 0 1 to 40 percent by weight of at least one saturated long chain fatty acid and/or its glycerol esters, or at least one saturated long chain fatty alcohols, or at least one dicarboxylic acid, or at least one sterol or mixtures thereof with (b) a liquid neutral organic compound, at a pressure in the range of 200 torr to 2500 torr

A process as claimed in claim 16 wherein the fatty acid has a chain length of C sub 10 to C sub 31

A process as claimed in claims 16 and 17 wherein a required part of the fatty acids or their glycerol esters or both or at least one saturated long chain fatty alcohols, or at least one dicarboxylic acid, or at least one sterol or mixtures thereof are taken in an appropriate vessel and heated till the substance melts and adding such molten fatty acids, glycerol esters of fatty acids or both, with a required part of the desired liquid neutral organic compound and mixing both the liquids to obtain the solidified composition

A process as claimed in claim 18 wherein the mixture is allowed to solidify at ambient temperature

A process as claimed in claim 18 wherein the mixture is allowed to cool and solidify at a temperature in the range of 2 deg C to 10 deg C

A process as claimed in claim 18 wherein the mixture is allowed to cool down at a controlled rate of 0 1 deg C to 1 deg C per minute to enhance thermal stability

A process as claimed in claim 16 wherein a said fatty acid can be selected from decanoic acid, hendecanoic acid, aminohendecanoic acid, dodecanoic acid, aminododecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, heneicosanoic acid, docosanoic acid, tπcosanoic acid, tetracosanoic acid, pentacosanoic acid, hexacosanoic acid, heptacosanoic acid, octacosanoic acid, nonacosanoic acid, tπacontanoic acid and hentπacontanoic acid

A process as claimed in claim 16 wherein the esters are selected from trilaurin, trimyristin, tripalmitin, tristearin and tπbehenin

A process as claimed in claim 16 the said liquid neutral organic compound is selected from vegetable oils, essential oils, mineral oils and neutral organic solvents A process as claimed in claim 24 wherein the said vegetable oil is selected from coconut oil, groundnut oil, olive oil, palm oil, mustard oil, sunflower oil, neem oil, cottonseed oil, rapeseed oil, soybean oil, sesame oil, corn oil, castor oil, safflower oil, rice bran oil, linseed oil, corn oil, poppy oil, fish oil, tall oil and tung oil

A process as claimed in claim 24 wherein the said essential oils are selected from mint oil, camphor oil, cinnamon oils, citrus oil, lemon oil, orange oil, Cyprus oil, eucalyptus oil, geranium oil, jasmine oil, lavender oil, lemon grass oil, linaloe oil, rose oil, sandalwood oil, turpentine oil, clove oil, pepper oil and cardamom oil

A process as claimed in claim 24 wherein the said mineral oils are selected from crude fossil oil, petroleum, diesel and kerosene.

A process as claimed in claim 24 wherein the said neutral organic solvents are selected from mono-, di- or tri-hydric alcohols, acetone acetonitrile, aniline, benzene, 1-butanol, 2-butanol, tert-butanol, iso-butanol, n-butyl acetate, carbon disulfide, cyclohexane, diethyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxan, ethanol, ethylacetate, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monomethylether, ethyl methyl ketone, methanol, propanol, pyridine, toluene and xylene.

A process as claimed in claims 16, 25, 26, 27 and 28 wherein 10% by Wt of kokum fat is required to solidify sunflower oil, 15% by Wt of kokum fat is required to solidify lavender oil, 20% by Wt. is required to solidify petrol, 20% by Wt is required to solidify kerosene and 20% by Wt is required to solidify acetone

A process as claimed in claim 16 wherein minimum quantity (percent, w/w) of fatty acid required for the solidification of organic liquids of different classes, decreased sharply with increasing chain-length of the solidifying agent from C sub 10 to C sub. 19 and remained more or less constant thereafter, and the melting temperature of the solidified mixture increased with increasing chain length of the fatty acid that is used as solidifying agent.

3 1 A process as claimed in claim 16 wherein the presence of an additional carboxylic acid group at the methyl end of decanoic acid (as in sebacic acid) is found to enhance the solidification ability by more than ten-fold over decanoic acid and the dicarboxylic acids (C sub. 6 to C sub. 10) solidified seed oils and essential oils.

32. A process for producing a novel, reversible and synergistic solid/semi-solid organic composition, said process comprising mixing (a) 0.1 to 40 percent by weight of at least one saturated long chain fatty acid and/or its glycerol esters, or at least one saturated long chain fatty alcohols, or at least one dicarboxylic acid, or at least one sterol or mixtures thereof with (b) a liquid neutral organic compound, at a pressure in the range of 200 torr to 2500 torr and thereby solidify the organic composition; liquefying the solid/semi-solid which is subjected to alkali treatment; filtering the mixture and thereby obtaining the ingredients (a) and (b).

33. A process as claimed in ciaim 32, wherein the solidified mixture is melted to its liquid state, to the molten mixture sodium hydroxide (aqueous sodium hydroxide solution) is added and stirred for 10 minutes, after the alkali treatment, the mixture is filtered to remove the salts of fatty acids, the filtrate (starting commodity) is recovered, excess or unreacted sodium hydroxide in the filtrate is removed by the addition of equal amount of hot water, stirred and allowed to settle, the aqueous layer is removed and discarded and the moisture in the oil is removed under reduced pressure.

34. A process as claimed in claim 32, wherein the solidified oil or solidified organic solvent is melted to liquefy the solid, the free fatty acid added for solidification is removed by the alkaline treatment as described in Example 22, concentrated hydrochloric acid (12 N) is added until the pH changed to acidic and the free fatty acid is separated by filtration, or the added fatty acids or their glycerol esters are recovered by fractional distillation.

A process as claimed in claim 32, wherein the solidified solid/semi-solid preparation is melted to liquid state and distilled thereby to separate the added solidifying agent or the solidified ingredient is recovered by conventional fractional distillation process.

AMENDED CLAIMS

[received by the International Bureau on 05 January 2001 (05.01.01); original claims 1 -35 replaced by new claims 1-58 (9 pages)]

1 A novel synergistic solid /semi-solid organic composition, comprising

5 i) at least one saturated long chain fatty acid, at least one saturated long chain fatty alcohols or at least one sterol or mixtures thereof, and ii) at least one neutral organic compound which is liquid at 2S°C, said ingredients (a) being present in a ratio between 0 1 to 40 percent by weight and the 10 remaining part from (b)

2 A composition as claimed in claim 1 wherein the fatty acid has a chain length from C sub.10 to C sub.31 l 3 A composition as claimed claim 1 wherein the said fatty acid can be selected from decanoic acid, hendecanoic acid, aminohendecanoic acid, dodecanoic acid, aminododecanoic acid, tπdecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, heneicosanoic acid, docosanoic acid, tπcosanoic acid,

20 tetracosanoic acid, pentacosanoic acid, hexacosanoic acid, heptacosanoic acid, octacosanoic acid, nonacosanoic acid, tπacontanoic acid and hentπacontanoic acid.

4 A composition as claimed in claim 1 wherein the saturated long-chain fatty 25 alcohols can be selected from C sub. 18 to C sub 30 fatty alcohols

5 A composition as claimed in claim 1 wherein the sterol can be selected from cholesterol or deoxycholic or cholic acid

30 6 A composition as claimed in claim 1 wherein the said liquid neutral organic compound can be selected from vegetable oils, essential oils, mineral oils and neutral organic solvents

7 A composition as claimed in claim 6 wherein the said vegetable oil can be

35 selected from coconut oil, groundnut oil, olive oil, palm oil, mustard oil, sunflower oil, neem oil, cottonseed oil, rapeseed oil, soybean oil, sesame oil, corn oil, castor oil, safflower oil, rice bran oil, linseed oil, corn oil, poppy oil, fish oil, till oil and tung oil.

8. A composition as claimed in claim 6 wherein the said essential oils can be selected from mint oil, camphor oil, cinnamon oils, citrus oil, lemon oil, orange oil, Cyprus oil, eucalyptus oil, geranium oil, jasmine oil, lavender oil, lemon grass oil, linolae oil, rose oil, sandalwood oil, turpentine oil, clove oil, pepper oil and cardamom oil.

9. A composition as claimed in claim 6 wherein the said mineral oils are selected from crude fossil oil, petroleum, diesel and kerosene.

10. A composition as claimed in claim 6 wherein the said neutral organic solvents are selected from mono-, di-, or tri-hydric alcohols, acetone, acetonitrile, aniline, benzene, 1-butanol, 2-butanol, tert-butanol, iso-butanol, n-butyl acetate, carbon disulfide, cyclohexane, diethyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxan, ethanol, ethylacetate, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monomethylether, ethyl methyl ketone, methanol, I-propanol, pyridine, toluene and xylene.

11. A composition as claimed in claims 1, 7, 8 and 9 wherein 15% by Wt. of kokum fat is required to solidify lavender oil, 20% by Wt. is required to solidify petrol, 20% by Wt. is required to solidify kerosene and 20% by Wt. is required to solidify acetone.

12. A novel synergistic solid /semi-solid organic composition, comprising. a) at least one glycerol esters; and b) one or more liquid organic compound selected from neutral mineral oil, neutral organic solvents or neutral essential oil, which compound is liquid at 25°C, said ingredients (a) being present in a ratio between 0.1 to 40 percent by weight and the remaining part from (b).

13. A composition as claimed in claim 12 wherein the glycerol esters can be selected from trilaurin, trimyristin, tripalmitin, tristearin and tribehenin or mixtures thereof.

14. A composition as claimed in claim 12 wherein the said essential oils can be selected from mini oil, camphor oil, cinnamon oils, citrus oil, lemon oil, orange oil, Cyprus oil, eucalyptus oil, geranium oil, jasmine oil, lavender oil, lemon grass oil, linolae oil, rose oil, sandalwood oil, turpentine oil, clove oil, pepper oil and cardamom oil.

15. A composition as claimed in claim 12 wherein the said mineral oils are selected from crude fossil oil, petroleum, diesel and kerosene.

16. A composition as claimed in claim 12 wherein the said neutral organic solvents are selected from mono-, di-, or tri-hydric alcohols, acetone, acetonitrile, aniline, benzene, 1-butanol, 2-butanol, tert-butanol, iso-butanol, n-butyl acetate, carbon disulfide, cyclohexane, diethyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxan, ethanol, ethylacetate, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monomethylether, ethyl methyl ketone, methanol, I-propanol, pyridine, toluene and xylene.

17. A novel synergistic solid /semi-solid organic composition, comprising: a) at least one dicarboxylic acid, and b) one or more organic compound selected from neutral mineral oil, neutral essential oil or neutral organic solvents, which compound is liquid at 25°C, said ingredients (a) being present in a ratio between 0.1 to 40 percent by weight and the remaining part from (b).

18. A composition as claimed in claim 17 wherein the dicarboxylic acids can be selected from C sub. 6 to C sub. 10 dicarboxylic acids.

19. A composition as claimed in claim 17 wherein the said essential oils can be selected from mint oil, camphor oil, cinnamon oils, citrus oil, lemon oil, orange oil, Cyprus oil, eucalyptus oil, geranium oil, jasmine oil, lavender oil, lemon grass oil, linolae oil, rose oil, sandalwood oil, turpentine oil, clove oil, pepper oil and cardamom oil.

20. A composition as claimed in claim 17 wherein the said mineral oils are selected from crude fossil oil, petroleum, diesel and kerosene.

21. A composition as claimed in claim 17 wherein the said neutral organic solvents are selected from mono-, di-, or tri-hydric alcohols, acetone, acetonitrile, aniline, benzene, 1-butanol, 2-butanol, tert-butanol, iso-butanol, n-butyl acetate, carbon disulfide, cyclohexane, diethyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxan, ethanol, ethylacetate, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monomethylether, ethyl methyl ketone, methanol, I-propanol, pyridine, toluene and xylene.

22. A novel synergistic solid /semi-solid organic composition, comprising: a) at least one saturated long chain hydroxyl ated fatty acids, and b) one or more neutral vegetable oils which is liquid at 25°C, said ingredients (a) being present in a ratio between 0.1 to 40 percent by weight and the remaining part from (b).

23. A composition as claimed in claim 22 wherein the saturated long chain hydroxylated fatty acids can be selected from C. sub.16 to C.sub.30.

24. A composition as claimed in claim 22 wherein the said vegetable oil can be selected from coconut oil, groundnut oil, olive oil, palm oil, mustard oil, sunflower oil, neem oil, cottonseed oil, rapeseed oil, soybean oil, sesame oil, corn oil, castor oil, safflower oil, rice bran oil, linseed oil, corn oil, poppy oil, fish oil, till oil and tung oil.

25. A process for producing a novel synergistic solid/semi-solid organic composition, said process comprising mixing (a) 0.1 to 40 percent by weight of at least one saturated long chain fatty acid, at least one saturated long chain fatty alcohols, or at least one sterol or mixtures thereof with (b) a neutral organic compound which is liquid at 25°C, at a pressure in the range of 200 torr to 2500 torr.

26. A process as claimed in claim 25 wherein the fatty acid has a chain length of C.sub. l0 to C.sub.31.

27. A process as claimed in claim 25 wherein a required part of the fatty acids, saturated long chain fatty alcohols, sterol or mixtures thereof are taken in an appropriate vessel and heated till the substance melts and adding such molten material with a required part of the desired liquid neutral organic compound and mixing both the liquids to obtain the solidified composition.

28. A process as claimed in claim 25 wherein the mixture is allowed to solidify at ambient temperature.

29. A process as claimed in claim 25 wherein the mixture is allowed to cool and solidify at a temperature in the range of 2°C to 10°C.

30. A process as claimed in claim 25 wherein the mixture is allowed to cool down at a controlled rate of 0.1°C to 1°C per minute to enhance thermal stability.

31. A process as claimed in claim 25 wherein a said fatty acid can be selected from decanoic acid, hendecanoic acid, aminohendecanoic acid, dodecanoic acid, aminododecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, heneicosanoic acid, docosanoic acid, tricosanoic acid, tetracosanoic acid, pentacosanoic acid, hexacosanoic acid, heptacosanoic acid, octacosanoic acid, nonacosanoic acid, triacontanoic acid and hentriacontanoic acid.

32. A process as claimed in claim 25 wherein the sterol can be selected from cholesterol or deoxycholic or cholic acid.

33. A process as claimed in claim 25 the said liquid neutral organic compound is selected from vegetable oils, essential oils, mineral oils and neutral organic solvents.

34. A process as claimed in claim 33 wherein the said vegetable oil is selected from coconut oil, groundnut oil, olive oil, palm oil, mustard oil, sunflower oil, neem oil, cottonseed oil, rapeseed oil, soybean oil, sesame oil, corn oil, castor oil, safflower oil, rice bran oil, linseed oil, corn oil, poppy oil, fish oil, tall oil and tung oil.

35. A process as claimed in claim 33 wherein the said essential oils are selected from mint oil, camphor oil, cinnamon oils, citrus oil, lemon oil, orange oil, Cyprus oil, eucalyptus oil, geranium oil, jasmine oil, lavender oil, lemon grass oil, linaloe oil, rose oil, sandalwood oil, turpentine oil, clove oil, pepper oil and cardamom oil.

36. A process as claimed in claim 33 wherein the said mineral oils are selected from crude fossil oil, petroleum, diesel and kerosene.

37. A process as claimed in claim 33 wherein the said neutral organic solvents are selected from mono-, di- or tri-hydric alcohols, acetone acetonitrile, aniline, benzene, 1-butanol, 2-butanol, tert-butanol, iso-butanol, n-butyl acetate, carbon disulfide, cyclohexane, diethyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxan, ethanol, ethylacetate, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monomethylether, ethyl methyl ketone, methanol, propanol, pyridine, toluene and xylene.

38. A process as claimed in claims 25, 34, 35 and 36 wherein 15% by Wt. of kokum fat is required to solidify lavender oil, 20% by Wt. is required to solidify petrol, 20% by Wt. is required to solidify kerosene and 20% by Wt. is required to solidify acetone.

39. A process as claimed in claim 25 wherein minimum quantity (percent, w/w) of fatty acid required for the solidification of organic liquids of different classes, decreased sharply with increasing chain-length of the solidifying agent from C sub. 10 to C sub. 19 and remained more or less constant thereafter, and the melting temperature of the solidified mixture increased with increasing chain length of the fatty acid that is used as solidifying agent.

40. A process as claimed in claim 25 wherein the presence of an additional carboxylic acid group at the methyl end of decanoic acid (as in sebacic acid) is found to enhance the solidification ability by more than ten-fold over decanoic acid and the dicarboxylic acids (C sub. 6 to C sub. 10) solidified seed oils and essential oils.

41. A process for producing a novel synergistic solid/semi-solid organic composition, said process comprising mixing (a) 0.1 to 40 percent by weight of glycerol esters with (b) a neutral organic compound which is liquid at 25°C, at a pressure in the range of 200 torr to 2500 torr.

42. A process as claimed in claim 41 wherein the glycerol esters can be selected from trilaurin, trimyristin, tripalmitin, tristearin and tribehenin or mixtures thereof.

43. A process as claimed in claim 41 the said liquid neutral organic compound is selected from essential oils, mineral oils and neutral organic solvents.

44. A process as claimed in claim 43 wherein the said essential oils are selected from mint oil, camphor oil, cinnamon oils, citrus oil, lemon oil, orange oil, cyprus oil, eucalyptus oil, geranium oil, jasmine oil, lavender oil, lemon grass oil, linaloe oil, rose oil, sandalwood oil, turpentine oil, clove oil, pepper oil and cardamom oil.

45. A process as claimed in claim 43 wherein the said mineral oils are selected from crude fossil oil, petroleum, diesel and kerosene.

46. A process as claimed in claim 43 wherein the said neutral organic solvents are selected from mono-, di- or tri-hydric alcohols, acetone acetonitrile, aniline, benzene, 1-butanol, 2-butanol, tert-butanol, iso-butanol, n-butyl acetate, carbon disulfide, cyclohexane, diethyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxan, ethanol, ethylacetate, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monomethylether, ethyl methyl ketone, methanol, propanol, pyridine, toluene and xylene.

47. A process for producing a novel synergistic solid/semi-solid organic composition, said process comprising mixing (a) 0.1 to 40 percent by weight at least one dicarboxylic acid with (b) a neutral organic compound which is liquid at 25°C, at a pressure in the range of 200 torr to 2500 torr.

48. A process as claimed in claim 47 wherein the dicarboxylic acids can be selected from C sub. 6 to C sub. 10 dicarboxylic acids.

49. A process as claimed in claim 47 the said liquid neutral organic compound is selected from essential oils, mineral oils and neutral organic solvents.

50. A process as claimed in claim 49 wherein the said essential oils are selected from mint oil, camphor oil, cinnamon oils, citrus oil, lemon oil, orange oil, cyprus oil, eucalyptus oil, geranium oil, jasmine oil, lavender oil, lemon grass oil, linaloe oil, rose oil, sandalwood oil, turpentine oil, clove oil, pepper oil and cardamom oil.

51. A process as claimed in claim 49 wherein the said mineral oils are selected from crude fossil oil, petroleum, diesel and kerosene.

52. A process as claimed in claim 49 wherein the said neutral organic solvents are selected from mono-, di- or tri-hydric alcohols, acetone acetonitrile, aniline, benzene, 1-butanol, 2-butanol, tert-butanol, iso-butanol, n-butyl acetate, carbon disulfide, cyclohexane, diethyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxan, ethanol, ethylacetate, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monomethylether, ethyl methyl ketone, methanol, propanol, pyridine, toluene and xylene.

53. A process for producing a novel synergistic solid/semi-solid organic composition, said process comprising mixing (a) 0.1 to 40 percent by weight of saturated long chain hydroxylated fatty acids can be selected from C.sub. 16 to C. sub.30 with (b) a neutral vegetable oil which is liquid at 25°C, at a pressure in the range of 200 torr to 2500 torr.

54. A process as claimed in claim 53 wherein the said vegetable oil can be selected from coconut oil, groundnut oil, olive oil, palm oil, mustard oil, sunflower oil, neem oil, cottonseed oil, rapeseed oil, soybean oil, sesame oil, corn oil, castor oil, safflower oil, rice bran oil, linseed oil, corn oil, poppy oil, fish oil, till oil and tung oil.

55. A process for producing a novel, reversible and synergistic solid/semi-solid organic composition, said process comprising mixing (a) 0.1 to 40 percent by weight of at least one saturated long chain fatty acid and or its glycerol esters, or at least one saturated long chain fatty alcohols, or at least one dicarboxylic acid, or at least one sterol or mixtures thereof with (b) a liquid neutral organic compound, at a pressure in the range of 200 torr to 2500 torr and thereby solidify the organic composition; liquefying the solid/semi-solid which is subjected to alkali treatment; filtering the mixture and thereby obtaining the ingredients (a) and (b).

56. A process as claimed in claim 55, wherein the solidified mixture is melted to its liquid state, to the molten mixture sodium hydroxide (aqueous sodium hydroxide solution) is added and stirred for 10 minutes, after the alkali treatment, the mixture is filtered to remove the salts of fatty acids, the filtrate (starting commodity) is recovered, excess or unreacted sodium hydroxide in the filtrate is removed by the addition of equal amount of hot water, stirred and allowed to settle, the aqueous layer is removed and discarded and the moisture in the oil is removed under reduced pressure.

57. A process as claimed in claim 55, wherein the solidified oil or solidified organic solvent is melted to liquefy the solid, the free fatty acid added for solidification is removed by the alkaline treatment as described in Example 22, concentrated hydrochloric acid (12 N) is added until the pH changed to acidic and the free fatty acid is separated by filtration, or the added fatty acids or their glycerol esters are recovered by fractional distillation.

58. A process as claimed in claim 55, wherein the solidified solid semi-solid preparation is melted to liquid state and distilled thereby to separate the added solidifying agent or the solidified ingredient is recovered by conventional fractional distillation process.

IN THE INTERNATIONAL BUREAU OF WIPO

In Re International Application of: NAGARJUNA HOLDINGS PRIVATE LIMITED

International Application No: PCT/INOO/00009

International filing date: February 4, 2000 (04.02.2000)

Title: NOVEL SYNERGISTIC SOLID/SEMI-SOLID ORGANIC COMPOSITION, A PROCESS OF PREPARING SUCH ORGANIC COMPOSITION AND A METHOD OF ALTERING PHYSICAL PROPERTIES OF LIQUID NEUTRAL ORGANIC COMPOUNDS AND THEIR MIXTURES

STATEMENT UNDER ARTICLE 19(1)

Regarding the first citation entitled Ηeat-Resistant Cocoa Butter Extenders from Mahua (Madhuca latifolia) and Kokum (Garcinia indica) Fats by JEYARANI, T., AND YELLA REDDY, Journal of the American Oil Chemists' Society., vol.76, no.12, 1999, pages 1431-1436, XP002149855, the applicants respectfully submit that the above citation relates to increasing the melting of the solid namely, cocoa butter which is solid at ambient temperature / room temperature. On the other hand, the aim of the present invention is to convert a liquid which is liquid at 25°C into a solid. The citation is specifically teaches how to raise the melting temperature of cocoa butter by the addition of triglycrides specifically a fraction enriched in stearic acid in positions 1 and 3 and oleic acid in position 2. Thus, a mixed triester comprising both saturated and unsaturated fatty acids^' are employed. The present invention does not employ any unsaturated fatty acids and it relates only to saturated fatty acids.

There is no suggestion or clue regarding solidification of a liquid which is liquid at 25°C in the citation. Claim 1 is now been amended to include the limitation of "neutral organic compound which is liquid at 25°C, which limitation has been clearly supported in the description and in the examples. In other words, no cocoa butter has been studied or claimed for solidification in the present invention. Cocoa butter is solid at ambient temperature and the teaches away from the present invention. In fact, the neutral organic compound which is liquid at 25°C is solidified in the present invention and any organic compound which is not liquid at 25°C is not in the part of the invention claimed. Claim 2 of the present application does not overlap with the above citation.

Claim 3 is totally out of the purview of the citation, since it covers only the saturated fatty acids and not the unsaturated fatty acids disclosed in the citation.

As regards claim 4, this claim is totally outside the scope of the above citation. The citation does not include a single fatty acid and in fact it claims a combination or mixtures of triglycride. In the present application, pure triesters of a single fatty acid is claimed.

With regard to claim 9, the present invention relates to neutral organic compound which is liquid at 25°C and does not relate to a cocoa butter which is solid at ambient temperature (25°C). In other words, claim 9 does not relate to any substage which is solid at ambient temperature, whereas cocoa butter is solid at that temperature and hence, the above citation is not application to this claim.

Regarding claim 11, this claim does not talk about cocoa butter which is solid at ambient temperature (25°C), in fact this claim relates to liquid oil which is liquid at 25°C.

As regards claim 15, this claim relates to use of a single ingredient i.e. Kokum fat as an additive to solidify an oil which is liquid at 25°C. On the other hand, the citation teaches increasing the melting temperature of cocoa butter which is solid at 25°C by adding a mixture namely Kokum fat and Mahua fat or the extenders. In other words, the present claim 15 is for solidifying an oil which is a liquid at 25°C using a Kokum fat and this aspect has not been envisaged in the above citation i.e. not for solidifying cocoa fat which is solid at 25°C. In addition, the above citation does not talk about reversibility of the solid form into liquid.

As regards claim 16 to 19, 22, 24 and 28, the citation is no way relating to these claims since the process relates to solidification of a neutral organic compound which is liquid at 25°C and not to a cocoa fat which is solid at 25°C.

Database WPI - XP002149856

This citation relates to employing a solidifying agent which is a partial ester exchanged reaction product. On the other hand, the present invention employs entirely a different additive to solidify a neutral compound which is liquid at 25°C. The present invention uses a naturally occurring product and not a product which is obtained by partial ester exchange reaction. The additives employed in the citation has altogether different chemical nature, which does not occur naturally or produced by partial ester exchange reaction. In the present invention, the additives used are not obtained by chemical reaction and they are occurring in nature. In fact, there is no overlapping at all between the present invention and the citation which teaches away from the invention.

US 4923 708

This citation relates to use of a fat bloom inhibitor comprising atieast one dicarboxylic acid to reduce the tendency of white and gray deposits on the surface of chocolate, hard butters, compound coatings and fat based compositions for extended periods of time. The products containing the fat bloom inhibitors further exhibit a prolonged gloss appearance which would otherwise become dull and hazy. On the other hand, the present invention relates to solidifying a neutral organic compound which is liquid at 25°C and the citation does not relates to solidifying a liquid at 25°C. The citation does not talk about use of saturated long chain fatty acid, long chain fatty alcohols or sterol or their mixtures in solidifying a neutral organic compound including mineral oils and essential oils. Still, claim 1 has been revised to eliminate the use of any dicarboxylic acid with vegetable oils in order to overcome any conflict.

GB 1 564363 A

This citation relates to a method of accelerating fat solidification. The method teaches solidification of a melt comprising a fat or a fat-containing preparation by dispersing a crystalline powder-form composition comprising triglycrides. On the other hand, the present invention relates to solidification of a neutral organic compound which is liquid at 25°C. The citation does not envisage use of saturated long chain fatty acids or saturated long chain fatty acids or sterol or the mixture and use of glycerol esters to solidify essential oils. Still, the claims have been suitably amended to distinguish the citation from the present invention.

Patent Abstracts of Japan - Publication No.61053212

This citation relates to use of an alkali or alkaline earth metal salt of stearic acid to solidify a hydrocarbon composition consisting of hydrocarbons and 12-hydroxystearic acid. The present invention does not use any alkali or alkaline earth metal salt of stearic acid to solidify a composition consisting of hydrocarbons and 12-hydroxystearic acid. The present invention is to solidify the neutral compound and not a composition. Nevertheless, the claims have been revised to overcome any anticipation.

Database WPI - XP 002149857

This citation is irrelevant to the present invention. The amendments to the claim even removes any stray overlapping of the subject matters.

The amendments made in the claims are fall in within the scope of the claims and in deed, the claims have been narrowed down from its original scope. There is no additional material or matter added in the claims.