WO2019230978A1 - A tannic acid based surface-active compounds - Google Patents

A tannic acid based surface-active compounds Download PDF

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WO2019230978A1
WO2019230978A1 PCT/JP2019/021877 JP2019021877W WO2019230978A1 WO 2019230978 A1 WO2019230978 A1 WO 2019230978A1 JP 2019021877 W JP2019021877 W JP 2019021877W WO 2019230978 A1 WO2019230978 A1 WO 2019230978A1
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tannic acid
tannaphile
active compounds
tannaphiles
based surface
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French (fr)
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Masahiko Abe
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Acteiive Corporation
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H13/00—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
    • C07H13/02—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
    • C07H13/08—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals directly attached to carbocyclic rings

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  • the present invention relates to a tannic acid based surface-active compounds, a method of producing tannic acid based surface-active compounds and a dispersing composition including the Tannic acid based surface-active compounds.
  • a tannic acid based surface-active compounds includes surfactant.
  • Non-Patent Literatures 1 to 3 The bio-based surfactant molecules in which the carbon atoms are derived from naturally occurring renewable feedstocks is good alternative to synthetic petrochemical based surfactants. In recent years environmental concerns such as ever-increasing CO 2 levels is also compelling to develop new generation of sustainable surfactant molecules based on natural structural motifs i.e. carbohydrates, fatty acids, fatty alcohols, amino acids etc.
  • Non-Patent Literatures 1 It has also been estimated that the use of oleochemicals for surfactant production may lead to greater CO 2 savings and if renewable surfactants replaces petrochemical surfactants the CO 2 emissions associated with surfactant production can be drastically reduced. Considering the importance of renewable surfactants for long-term sustainable development we have developed new generation of tannic acid based surface-active compounds or surfactants called ‘Tannaphiles’.
  • a tannic acid based surface-active compounds of present invention is comprising one of the following chemical formulas (1) to (5).
  • a tannic acid based surface-active compounds of present invention is comprising of a hydrophobic group of tannic acid and a hydrophibic group of aliphatic alcohol.
  • the aliphatic alcohol has C12, C14, C16 or C18.
  • a method of producing tannic acid based surface-active compounds of present invention is comprising synthesizing plant-based tannic acid and aliphatic alcohol and filtering the synthesized material to obtain tannic acid based surface-active compounds.
  • a dispersing composition of present invention is comprising of containing the tannic acid based surface-active compounds in accordance with claim 1 or claim 2.
  • Fig. 1 is showing different isomers structures of tannic acid by 1(a), 1(b), 1(c) and 1(d).
  • Fig. 2 is showing different isomers end product structures of tannic acid based surface-active compounds by 2(a), 2(b) and 2(c).
  • Fig. 3 is showing 1 H NMR spectra of C12 Tannaphile recorded in mixture of MeOH-d 4 (500 ⁇ l) + DMSO-d 6 (100 ⁇ l). The structure shown along with 1 H NMR spectra is just one probable molecule in mixture of different isomers. The point of attachment of hydrophobic tail varies, as hydrophobic tail can be present randomly attached to any pentagalloyl moiety.
  • the chemical shift of standard deuterated solvent demonstrate some shift from their respective original values with respect to TMS due to mixed deuterated solvent system adopted for analyzing the sample.
  • Fig. 4 is showing 1 H- 1 H Homonuclear COSY spectra of C12 Tannaphile.
  • Fig. 5 is showing 1 H NMR spectra of (a) C14 Tannaphile and (b) C16 Tannaphile recorded in mixture of MeOH-d 4 (500 ⁇ l) + DMSO-d 6 (100 ⁇ l).
  • the chemical shift of standard deuterated solvent demonstrate some shift from their respective original values with respect to TMS due to mixed deuterated solvent system adopted for analyzing the sample.
  • Fig. 4 is showing 1 H- 1 H Homonuclear COSY spectra of C12 Tannaphile.
  • Fig. 5 is showing 1 H NMR spectra of (a) C14 Tannaphile and (b) C16 Tannaphile recorded in mixture of MeOH-d 4 (500 ⁇ l) +
  • Fig. 6 is showing (a) 13 C spectra of C12 Tannaphile and (b) DEPT-45 spectra of C12 Tannaphile.
  • Fig. 7 is showing plot of surface tension versus log of concentration plot of C12 Tannaphile at 25 degrees Celsius.
  • Fig. 8 is showing graphical representation of interacting micelles of Tannaphile in aqueous solution by (a) Tannaphile monomer, (b) Tannaphile micelles and (c) Graphical representation of interacting micelles of Tannaphile in aqueous solution.
  • FIG. 9 is showing size distribution of Tannaphile micelles at 25 degrees Celsius by (a) size distribution function based on intensity weight %, (b) size distribution function based on number weight % and (c) size distribution function based on volume weight %.
  • Fig. 10 is showing zeta potential distribution of Tannaphile micelles at 25 degrees Celsius by (a) 0.50wt.% (b) 1.00wt.% and (c) 2.00 wt.% in water.
  • Fig. 11 is showing proton NMR of micellar solution of C12 Tannaphile investigated in mixed polar deuterated solvent system (300 ⁇ l D 2 O and 500 ⁇ l CD 3 OD) at 25 degrees Celsius.
  • Fig. 10 is showing zeta potential distribution of Tannaphile micelles at 25 degrees Celsius by (a) 0.50wt.% (b) 1.00wt.% and (c) 2.00 wt.% in water.
  • Fig. 11 is showing proton NMR of micellar solution of C12
  • Fig. 12 is showing an isomer end product structure of tannic acid based surface-active compounds.
  • Fig. 13 is showing viscosity vs. shear rate curves of C12 Tannaphile solution by (a) 0.25wt%, (b) 0.50wt%, (c) 1.00wt% and (d) 2.00 wt% in water.
  • a tannic acid based surface-active compounds A method of producing tannic acid based surface-active compounds, A dispersing composition including the Tannic acid based surface-active compounds will be described below.
  • a tannic acid based surface-active compounds A method of producing tannic acid based surface-active compounds: Molecular structure of surface-active - ‘Tannaphiles’ with respect to tannic acid isomers and synthetic scheme for synthesis of ‘Tannaphiles’:
  • fatty alcohols i.e. lauryl alcohol, myristyl alcohol, cetyl alcohol and stearyl alcohol
  • bromoacetic acid in the presence of p-toluenesulfonic acid as catalyst to get respective bromoesters i.e. lauryl 2-bromoacetate, myristyl 2-bromoacetate, cetyl 2-bromoacetate and stearyl 2-bromoacetate.
  • bromoesters i.e. lauryl 2-bromoacetate, myristyl 2-bromoacetate, cetyl 2-bromoacetate and stearyl 2-bromoacetate.
  • oleyl alcohol is reacted with bromoacetic acid in the absence of p-toluenesulfonic acid to get oleyl 2-bromoacetate.
  • Tannic acid is naturally occurring plant polyphenols and is composed of esters of varying gallic acid molecules and a glucose moiety and is generally described as glucose pentagalloylgallate or 1,2,3,4,6-penta-O- ⁇ 3,4-dihydroxy-5-[(3,4,5-trihydroxybenzoyl)oxy]benzoyl ⁇ -D-glucopyranose ( Figure 1(a)). However it is actually mixture of different isomers and partially galloylated glucose ( Figure 1(b), 1(c), 1(d)).
  • surfactants derived from the commercial tannic acid also consist of mixtures of isomers.
  • individual tannic acid isomer surfactant if we use high purity individual isomer as starting material for synthesis of surfactant.
  • Chemical scheme (6) describes synthesis of C12 Tannaphile starting from glucose pentagalloylgallate (see Fig. 1(a)).
  • Tannaphiles such as C14 Tannaphile, C16 Tannaphile, C18 Tannaphile, C18:1 Tannaphile has been developed based on synthetic scheme (6) by reacting pentagalloylgallate (see Fig. 1(a)) with different long tail bromoesters i.e. myristyl 2-bromoacetate, cetyl 2-bromoacetate, stearyl 2-bromoacetate and oleyl 2-bromoacetate.
  • the point of attachment of hydrophobic tail is random and scheme (6) shows just one of the possibility.
  • the number of potassium ions present in the Tannaphiles is random and the number varies.
  • C12 Tannaphile can also be synthesized starting from pentagalloyl glucose or ⁇ -1,2,3,4,6-pentagalloyl-O-D-glucopyranose (PGG).
  • Chemical scheme (7) shows synthetic methodology for synthesis of C12 Tannaphile starting from PGG.
  • the partially hydrolyzed tannic acid derivatives are particularly found in tannic acid derived from Chinese gallnut, therefore partially hydrolyzed C12 Tannaphiles (see Fig. 2(b) and 2(c)) are obtained in certain ratio if tannic acid derived from Chinese gallnut is used as starting material for synthesis of C12 Tannaphiles.
  • C12 Tannaphiles are particularly found in tannic acid derived from Chinese gallnut, therefore partially hydrolyzed C12 Tannaphiles (see Fig. 2(b) and 2(c)) are obtained in certain ratio if tannic acid derived from Chinese gallnut is used as starting material for synthesis of C12 Tannaphiles.
  • other plant materials are useful; for instance Tara Pods from Tara Spinosa or Tara Plant and Gallnuts from Quercus Infectoria or Gallnut Plant.
  • Tannaphiles are synthesized starting from tannic acid.
  • Tannaphiles Different types of Tannaphiles have been synthesized differing in hydrophobic tail length. 2) The point of attachment of hydrophobic tail part is random. 3) The Tannaphile molecule may or may not contain potassium ions as a part of structure. 4) The number of potassium ions may differ depending on amount of potassium carbonate used during reaction for synthesizing Tannaphiles. 5) Small amount of dimeric and trimeric derivatives may present in sample. 6) The chemical process can be modified to get several dimeric and trimeric derivatives of tannaphiles.
  • Tannic acid was purchased from different suppliers Sigma Aldrich, Wako pure chemical industries etc. that consists of different isomers of tannic acid. Lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, bromoacetic acid and p-toluenesulfonic acid were purchased from TCI Chemicals. All solvents were purchased from Wako pure chemical industries. NMR solvents were purchased from Sigma Aldrich.
  • the reaction is further stirred for another 150 minutes (total time 5 hours including addition time).
  • the reaction mixture is then filtered and the DMF is removed by rotary evaporator under reduced pressure/high vacuum.
  • the solid mass thus obtained after removal of DMF is treated with 150ml of ethyl acetate by heating at 40 degrees Celsius for 5 minutes and then filtered to remove ethyl acetate.
  • the solid mass is again dissolved in 100ml ethyl acetate and the process is repeated.
  • the solid mass thus obtained after filtration is dried under reduced pressure in rotary evaporator to get tannic acid based surfactant – C12Tannaphiles.
  • C16 Tannaphiles Tannic acid (21.8 g) is dissolved in 120 ml dry dimethylformamide (DMF) by heating at 40 degrees Celsius under inert condition (nitrogen gas atmosphere). The solvent containing dissolved tannic acid is allowed to cool at room temperature. To the stirred solution of tannic acid, dry anhydrous potassium carbonate (11.14 g) is added under inert condition. Further, cetyl 2-bromoacetate (17.44 g) dissolved in 120 ml of dry DMF is slowly added drop wise to the reaction mixture under inert conditions over 150 minutes time frame at 20-25 degrees Celsius. The reaction is further stirred for another 150 minutes (total time 5 hours including addition time). The purification is done by following the same procedure described for purification for C12 Tannaphiles.
  • DMF dry dimethylformamide
  • Tannaphiles Characterization of Tannaphiles by 1D and 2D NMR Spectroscopy The molecular structure of the Tannaphiles synthesized from tannic acid has been established by both 1D ( 1 H, 13 C, 13 C APT and 13 C DEPT) and 2D (COSY and HETCOR) NMR spectroscopy.
  • C12 Tannaphiles are designated based on 2D 1 H- 1 H Homonuclear COSY spectroscopy.
  • the 1 H NMR spectral data of C12 Tannaphiles recorded in deuterated solvent mixture of MeOH-d 4 (500 ⁇ l) and DMSO-d 6 (100 ⁇ l) shows different sets of proton resonances.
  • the aromatic protons of galloyl moieties were observed downfield in-between ⁇ 6.83 to 7.49 ppm.
  • H-1 of central glucose moiety was observed at ⁇ 6.34 ppm, while H-2 was observed along with H-4 as multiplet at ⁇ 5.65 ppm.
  • H-3 of central glucose moiety was observed at ⁇ 6.00 ppm.
  • protons of central glucose moiety (H-4, H-5 and H-6) appear merged with the methylene protons (protons present on either side of ester functional group of hydrophobic alkyl tail) of C12 Tannaphile in between ⁇ 4.07 – 4.61 ppm.
  • the signal at ⁇ 4.80 ppm is because of partially hydrolyzed tannic acid moiety present as isomer.
  • the triplet observed at ⁇ 3.53 ppm is because of hydrolyzed lauryl alcohol present as inseparable impurity with C12 Tannaphile.
  • H-5 and H-6 (2H) demonstrate some peculiarities in the observed results which may be due to the inherent nature of these protons since flexibility of the galloyl moiety linked to the C6 methylene group is different compared to other protons whose mobility is restricted by their reciprocal steric hindrance (refer to reference 3). Moreover the sensitivity and chemical shifts of these protons greatly depend on choice of NMR solvents.
  • the molecular structure of the Tannaphiles has been further established by 13 C NMR spectroscopy.
  • Each individual type of carbon present in the molecular structure of C12 Tannaphiles can be distinguished by detailed carbon NMR analysis by custom 13 C NMR and DEPT analysis.
  • Figure 6 show 13 C NMR and DEPT 45 spectra of C12 Tannaphile.
  • the DEPT 45 spectrum distinguishes quaternary carbon from other carbons i.e. CH, CH 2 and CH 3 as signal for quaternary carbon is not observed in DEPT.
  • the characteristic peak for the methylene carbon -O C H 2 COOCH 2 - which is also the source peak for the point of attachment of tannic acid with hydrophobic tail appeared at ⁇ 71.2 ppm in all the spectrum. The position of this peak is also confirmed from 2D 1 H- 13 C HETCOR.
  • the characteristic peak for the aromatic CH carbon of the galloyl moiety appeared in-between ⁇ 107.5-108.2 ppm.
  • the other quaternary carbon of aromatic ring and carbonyl groups are not observed in DEPT spectrum however they are evident in 13 C spectrum.
  • the signal for traces of lauryl alcohol that is associated with C12 Tannaphiles is also visible in 13 C NMR spectra at ⁇ 60.3 ppm.
  • the signal for central glucose moiety of the C12 Tannaphiles are visible between ⁇ 63.3-69.4 ppm however the signal intensities of these signal are less compared to other carbon signals. This may be due to mobility restriction due to steric hindrance.
  • the critical micelle concentration of C12 Tannaphile is determined by surface tension measurements.
  • C12 Tannphile demonstrated ability to form micelle at very low surfactant concentration.
  • the cmc value of C12 Tannphile is 0.0102 wt.% (102 mg per liter) in aqueous solution.
  • the affinity to reduce surface tension at cmc (gamma cmc) is 33.1 mNm-1.
  • the evaluated cmc value of C12 Tannaphile is much lower compared to commercially available anioic surfactants like sodium dodecyl sulfate (SDS), sodium lauryl sulfoacetate (SLSA) and alkylbenzenesulfonate (BAS) surfactants.
  • SDS sodium dodecyl sulfate
  • SLSA sodium lauryl sulfoacetate
  • BAS alkylbenzenesulfonate
  • the C12 Tannphile also demonstrates excellent foaming ability at very low surfactant concentration of 0.02 wt.% (above its cmc value).
  • Tannaphile micelles demonstrate unique ability to interact in aqueous solution by: (i) ⁇ - ⁇ interaction (ii) Ion- ⁇ interaction (iii) Hydrogen Bonding
  • Tannaphile micelles Intra/Intermicellar interaction of Tannaphile micelles is investigated by: (i) Dynamic Light Scattering Measurements (ii) Zeta Potential Experiments (iii) NMR Experiments
  • Hydrodynamic radius of the micelles formed by C12 Tannaphile is determined by dynamic light scattering technique.
  • Figure 9 shows the size distribution of micelles formed by the C12 Tannaphile for different surfactant concentration determined at 25 degrees Celsius. The results indicate that the aggregates with different sizes and morphologies are formed depending on surfactant concentration. Two merged broad peaks are observed for the micellar solution of C12 Tannaphile at different surfactant concentrations (i.e. 0.25 wt.%, 0.50 wt.%, 1.00 wt.% and 2.00 wt.% in water).
  • the average hydrodynamic radius varies from 34 to 58 nm depending on surfactant concentration.
  • the observed results indicate that the C12 Tannaphile are able to form different structural morphologies by intra/inter-miceller interactions by varying the concentration.
  • the intra/inter micellar interactions modify the free diffusion of micelles and this leads to non-specific aggregation that modifies the observed size distribution.
  • the intra and inter micellar interactions is evident by the observed results investigated by Zeta Potential Experiments and NMR experiments (discussed later).
  • H Zeta Potential Distribution of C12 Tannaphile in Water at Different Concentration (see Fig. 10)
  • the ⁇ -Potential peaks exhibit broadening probably due to the presence intra/intermicellar interaction of C12 Tannaphile micelles as a result of ⁇ - ⁇ interaction between the galloyl moieties of headgroup, ion- ⁇ interaction between charged ions and galloyl moiety, hydrogen- ⁇ interaction, and hydrogen bonding between polar functional groups present within molecules as well as between polar functional groups and water molecules.
  • These type of non-covalent interactions significantly alters observed zeta potential with change in Tannaphile concentration in water.
  • the ⁇ -potential is often used as an index of the magnitude of electrostatic interaction between colloidal particles and is thus a measure of the colloidal stability of the solution.
  • mice with a ⁇ -potential less than -15 mV or more than 15 mV are expected to be stable from electrostatic considerations. It has been found in our studies that upon increasing the concentration of C12 Tannaphiles in aqueous solution the absolute ⁇ -potential values drastically changes. The ⁇ -potential distributions observed here are probably due to strong intra/intermicellar interaction of C12 Tannaphile micelles by non-covalent interactions such as ⁇ - ⁇ interaction between the galloyl moieties of headgroup, ion- ⁇ interaction between charged ions and galloyl moiety, hydrogen- ⁇ interaction, and hydrogen bonding between polar functional groups present within molecules as well as between polar functional groups and water molecules. Such interactions significantly alter the shape, size and ⁇ -potential distributions of micelles. This has been investigated in detail by NMR spectroscopy discussed in next section.
  • methylene protons (e,d and 6) and methine proton (5) demonstrate significant downfield chemical shift along with significant change in observed NMR signal due to inter micellar hydrogen bonding (see ig. 12).
  • the dispersing composition the method of dispersing crude oil emulsion, the method of dispersing asphaltene contained in crude oil and the method of s dispersing asphaltene contained in asphalt cement of the present invention are described bellow.
  • the dispersing composition is comprising of containing the tannic acid based surface-active compounds Tannaphile in a solution like aqueous.
  • the dispersing composition may be made as the Dilute Aqueous Solution of Tannaphile.
  • Viscosity Measurements of the Dilute Aqueous Solution of Tannaphile (see Fig. 13) The viscosities of the micellar solution of C12 Tannaphile were investigated by rheometer for different concentrations at 25degrees Celsius. The aqueous micellar solution of C12 Tannaphile demonstrated Newtonian fluid behavior between 0.25-2.00 wt.% since the observed viscosities are independent of the applied shear rate.
  • Figure 13 shows viscosity ( ⁇ ) vs. shear-rate ( ⁇ ) plot for the aqueous micellar solution of the C12 Tannaphile surfactants at 25degrees Celsius for various concentrations from 0.25wt.% to 2.00wt.%. The aqueous micellar solution of Tannaphile demonstrated Newtonian fluid behavior as the observed viscosities are independent of the applied shear rate.
  • the method of dispersing crude oil emulsion is comprising of putting crude oil emulsion into the above-mentioned dispersing solution then vibrating or mixing the dispersing solution and the crude oil emulsion to disperse the crude oil emulsion into the dispersing solution.
  • Tannaphile has demonstrated promising capability to solubilize crude oil in aqueous system and hence can be used for Enhanced Oil Recovery Application.
  • Crude oil is stable emulsion of oil fractions-asphaltene-petroleum waxes of high viscosity and hence very difficult to extract out of petroleum reservoir. Often treatment with some selective chemicals affords enhanced oil recovery.
  • Tannaphile is very effective in solubilizing oils by using it in accordance with the method of dispersing crude oil emulsion of present invention.
  • crude oil is stable emulsion oil, asphaltene and waxes along with traces of some metal impurities. It is very viscous and difficult to extract from petroleum reservoir.
  • Example 1 For instant result we have used 2wt.% Tannaphile solution as a dispersing solution of present invention. Treatment with dilute solution (0.25-0.5%) requires incubation time of 5-10 minutes before crude oil starts solubilizing in aqueous Tannaphile solution. After 5-10 minutes from the start of vibrating or mixing, the crude oil emulsion has dispersed finely into the dispersing solution.
  • Example 2 Tannaphile Based Dispersing Agent for Cleanup of Oil Spills by following steps. Step 1: Spraying Tannaphile based oil dispersing agent on the oil spills area in the sea, lakes, rivers and so on. Step 2: Tannaphile can break oil into small droplets. Step 3: Small dispersed oil droplets may be more readily biodegraded by microbes. Step 4: Tannaphiles can be easily degraded due to its biocompatible nature offering complete cleanup of organic residue.
  • Oil spill is the release crude or processed hydrocarbon into marine ecosystem which causes great harm to environment and ecosystem.
  • the present invention can solve these Oil spill problem easily.
  • Example 3 Tannaphile Based Dispersing Agent for Sending out Crude Oil Component from the Crude Oil Layer by following steps. Step 1: Injecting Tannaphile based oil dispersing agent with high pressure into a crude oil layer underground, Step 2: Dispersing a crude oil component of the crude oil layer into the dispersing solution. Step 3: Sending out the dispersing solution and the crude oil component from the crude oil layer.
  • Tannaphile can disperse crude oil into fine droplets in water it can be effectively used as oil dispersing agent and deal with the oil spill problem and difficulty of sending out crude oil component. Also since Tannaphile is based on natural structural design it will be better than several synthetic dispersing agent currently being used.
  • the method of dispersing asphaltene contained in crude oil is comprising putting crude oil emulsion into the dispersing solution containing the above-mentioned dispersing composition and vibrating or mixing the dispersing solution and the crude oil emulsion to disperse the asphaltene from the crude oil emulsion.
  • Example 1 Tannaphile Based Dispersing Agent for Dispersing Asphaltene contained in Crude Oil by following steps. Step 1: Putting crude oil emulsion into Tannaphile based oil dispersing agent. Step 2: Vibrating or mixing the Tannaphile based oil dispersing agent and the crude oil emulsion. Step 3: Dispersing the asphaltene from the crude oil emulsion.
  • the present invention can disperse the asphaltene from the crude oil emulsion easily.
  • the method of dispersing asphaltene contained in asphalt cement is comprising contacting the dispersing solution containing the dispersing composition according to claim 4 and asphalt cement and vibrating or mixing the dispersing solution and the asphalt cement together with heating them to disperse the asphaltene from the asphalt cement.
  • Example 1 Tannaphile Based Dispersing Agent for Dispersing Asphaltene contained in Asphalt Cement by following steps. Step 1: Contacting the Tannaphile based oil dispersing agent and asphalt cement. Step 2: Vibrating or mixing Tannaphile based oil dispersing agent and the asphalt cement together with heating them. Step 3: Dispersing the asphaltene from the asphalt cement.
  • the present invention can disperse the asphaltene from the asphalt cement easily.

Abstract

The present invention provides a tannic acid based surface-active compounds, a method of producing tannic acid based surface-active compounds and a dispersing composition including the Tannic acid based surface-active compounds. Considering the importance of renewable surfactants for long-term sustainable development we have developed new generation of tannic acid based surface-active compounds or surfactants called 'Tannaphiles'. Tannaphiles are very useful and can solve problems concerning crude oil easily.

Description

A TANNIC ACID BASED SURFACE-ACTIVE COMPOUNDS
The present invention relates to a tannic acid based surface-active compounds, a method of producing tannic acid based surface-active compounds and a dispersing composition including the Tannic acid based surface-active compounds.
In this specification, a tannic acid based surface-active compounds includes surfactant.
The use of synthetic surfactants is rapidly increasing with each passing year and the surface-active compounds are the highest volume synthetic chemicals currently being produced globally. Considering the wide range of application areas of these surface-active compounds ranging from industrial to consumer goods along with their ever-increasing demand, it is urgently required to develop new generation of sustainable surfactants based on renewable feedstocks (refer to Non-Patent Literatures 1 to 3). The bio-based surfactant molecules in which the carbon atoms are derived from naturally occurring renewable feedstocks is good alternative to synthetic petrochemical based surfactants. In recent years environmental concerns such as ever-increasing CO2 levels is also compelling to develop new generation of sustainable surfactant molecules based on natural structural motifs i.e. carbohydrates, fatty acids, fatty alcohols, amino acids etc.
P. Foley, A. K. Pour, E. S. Beach and J. B. Zimmerman, Chem. Soc. Rev., 2012, 41, 1499-1518. D. Blunk, P. Bierganns, N. Bongartz, R. Tessendorf and C. Stubenrauch, New Journal of Chemistry, 2006, 30, 1705. C. Gozlan, E. Deruer, M.-C. Duclos, V. Molinier, J.-M. Aubry, A. Redl, N. Duguet and M. Lemaire, Green Chem., 2016, 18, 1994-2004.
SUMMARY OF THE INVENTION
Recent studies have established that using renewable plant based or other natural origin based feedstocks significantly reduces the CO2 emissions associated with the production and use of surfactants. (refer to Non-Patent Literatures 1) It has also been estimated that the use of oleochemicals for surfactant production may lead to greater CO2 savings and if renewable surfactants replaces petrochemical surfactants the CO2 emissions associated with surfactant production can be drastically reduced. Considering the importance of renewable surfactants for long-term sustainable development we have developed new generation of tannic acid based surface-active compounds or surfactants called ‘Tannaphiles’.
MEANS FOR SOLVING PROBLEM
To achieve the above-described object, a tannic acid based surface-active compounds of present invention is comprising one of the following chemical formulas (1) to (5).
Figure JPOXMLDOC01-appb-I000002
To achieve the above-described object, a tannic acid based surface-active compounds of present invention is comprising of a hydrophobic group of tannic acid and a hydrophibic group of aliphatic alcohol.
The aliphatic alcohol has C12, C14, C16 or C18.
To achieve the above-described object, a method of producing tannic acid based surface-active compounds of present invention is comprising synthesizing plant-based tannic acid and aliphatic alcohol and filtering the synthesized material to obtain tannic acid based surface-active compounds.
To achieve the above-described object, a dispersing composition of present invention is comprising of containing the tannic acid based surface-active compounds in accordance with claim 1 or claim 2.
Fig. 1 is showing different isomers structures of tannic acid by 1(a), 1(b), 1(c) and 1(d). Fig. 2 is showing different isomers end product structures of tannic acid based surface-active compounds by 2(a), 2(b) and 2(c). Fig. 3 is showing 1H NMR spectra of C12 Tannaphile recorded in mixture of MeOH-d4 (500 μl) + DMSO-d6 (100 μl). The structure shown along with 1H NMR spectra is just one probable molecule in mixture of different isomers. The point of attachment of hydrophobic tail varies, as hydrophobic tail can be present randomly attached to any pentagalloyl moiety. The chemical shift of standard deuterated solvent demonstrate some shift from their respective original values with respect to TMS due to mixed deuterated solvent system adopted for analyzing the sample. Fig. 4 is showing 1H-1H Homonuclear COSY spectra of C12 Tannaphile. Fig. 5 is showing 1H NMR spectra of (a) C14 Tannaphile and (b) C16 Tannaphile recorded in mixture of MeOH-d4 (500 μl) + DMSO-d6 (100 μl). The chemical shift of standard deuterated solvent demonstrate some shift from their respective original values with respect to TMS due to mixed deuterated solvent system adopted for analyzing the sample. Fig. 6 is showing (a) 13C spectra of C12 Tannaphile and (b) DEPT-45 spectra of C12 Tannaphile. Fig. 7 is showing plot of surface tension versus log of concentration plot of C12 Tannaphile at 25 degrees Celsius. Fig. 8 is showing graphical representation of interacting micelles of Tannaphile in aqueous solution by (a) Tannaphile monomer, (b) Tannaphile micelles and (c) Graphical representation of interacting micelles of Tannaphile in aqueous solution. Fig. 9 is showing size distribution of Tannaphile micelles at 25 degrees Celsius by (a) size distribution function based on intensity weight %, (b) size distribution function based on number weight % and (c) size distribution function based on volume weight %. Fig. 10 is showing zeta potential distribution of Tannaphile micelles at 25 degrees Celsius by (a) 0.50wt.% (b) 1.00wt.% and (c) 2.00 wt.% in water. Fig. 11 is showing proton NMR of micellar solution of C12 Tannaphile investigated in mixed polar deuterated solvent system (300 μl D2O and 500 μl CD3OD) at 25 degrees Celsius. Fig. 12 is showing an isomer end product structure of tannic acid based surface-active compounds. Fig. 13 is showing viscosity vs. shear rate curves of C12 Tannaphile solution by (a) 0.25wt%, (b) 0.50wt%, (c) 1.00wt% and (d) 2.00 wt% in water.
DESCRIPTION OF EMBODIMENT
A tannic acid based surface-active compounds, A method of producing tannic acid based surface-active compounds, A dispersing composition including the Tannic acid based surface-active compounds will be described below.
A tannic acid based surface-active compounds, A method of producing tannic acid based surface-active compounds:
Molecular structure of surface-active - ‘Tannaphiles’ with respect to tannic acid isomers and synthetic scheme for synthesis of ‘Tannaphiles’:
These new surfactants have been developed in a two-step synthetic process. In the first step commercially available fatty alcohols (i.e. lauryl alcohol, myristyl alcohol, cetyl alcohol and stearyl alcohol) are reacted with bromoacetic acid in the presence of p-toluenesulfonic acid as catalyst to get respective bromoesters i.e. lauryl 2-bromoacetate, myristyl 2-bromoacetate, cetyl 2-bromoacetate and stearyl 2-bromoacetate. Alternately oleyl alcohol is reacted with bromoacetic acid in the absence of p-toluenesulfonic acid to get oleyl 2-bromoacetate. These alkyl 2-bromoacetates and oleyl 2-bromoacetate synthesized in first step is reacted with tannic acid in the presence of potassium carbonate in dimethyl formamide solvent to get tannic acid based surfactants called ‘Tannaphiles’. These molecules demonstrate excellent surface activity in aqueous solution.
Tannic acid is naturally occurring plant polyphenols and is composed of esters of varying gallic acid molecules and a glucose moiety and is generally described as glucose pentagalloylgallate or 1,2,3,4,6-penta-O-{3,4-dihydroxy-5-[(3,4,5-trihydroxybenzoyl)oxy]benzoyl}-D-glucopyranose (Figure 1(a)). However it is actually mixture of different isomers and partially galloylated glucose (Figure 1(b), 1(c), 1(d)).
Therefore surfactants derived from the commercial tannic acid also consist of mixtures of isomers. However it is possible to get individual tannic acid isomer surfactant if we use high purity individual isomer as starting material for synthesis of surfactant. Chemical scheme (6) describes synthesis of C12 Tannaphile starting from glucose pentagalloylgallate (see Fig. 1(a)).
Figure JPOXMLDOC01-appb-I000003
Similarly other derivatives of Tannaphiles such as C14 Tannaphile, C16 Tannaphile, C18 Tannaphile, C18:1 Tannaphile has been developed based on synthetic scheme (6) by reacting pentagalloylgallate (see Fig. 1(a)) with different long tail bromoesters i.e. myristyl 2-bromoacetate, cetyl 2-bromoacetate, stearyl 2-bromoacetate and oleyl 2-bromoacetate. The point of attachment of hydrophobic tail is random and scheme (6) shows just one of the possibility. Also the number of potassium ions present in the Tannaphiles is random and the number varies.
Similarly the C12 Tannaphile can also be synthesized starting from pentagalloyl glucose or β-1,2,3,4,6-pentagalloyl-O-D-glucopyranose (PGG). Chemical scheme (7) shows synthetic methodology for synthesis of C12 Tannaphile starting from PGG.
Figure JPOXMLDOC01-appb-I000004
However since commercially available tannic acid is composed of different types of isomers depending on source of tannic acid, the following C12 Tannphiles are also obtained as isomeric end product (Figure 2).
The partially hydrolyzed tannic acid derivatives are particularly found in tannic acid derived from Chinese gallnut, therefore partially hydrolyzed C12 Tannaphiles (see Fig. 2(b) and 2(c)) are obtained in certain ratio if tannic acid derived from Chinese gallnut is used as starting material for synthesis of C12 Tannaphiles. Also other plant materials are useful; for instance Tara Pods from Tara Spinosa or Tara Plant and Gallnuts from Quercus Infectoria or Gallnut Plant.
A: Summarization of Chemical Structures of Various Tannaphiles Synthesized
Tannic acid based surface-active compounds of present invention are comprising one of the following chemical schemes (1) to (5).
Figure JPOXMLDOC01-appb-I000005
Various different types of Tannaphiles are synthesized starting from tannic acid. Here we have summarized several structural features of the Tannaphiles:
1) Different types of Tannaphiles have been synthesized differing in hydrophobic tail length.
2) The point of attachment of hydrophobic tail part is random.
3) The Tannaphile molecule may or may not contain potassium ions as a part of structure.
4) The number of potassium ions may differ depending on amount of potassium carbonate used during reaction for synthesizing Tannaphiles.
5) Small amount of dimeric and trimeric derivatives may present in sample.
6) The chemical process can be modified to get several dimeric and trimeric derivatives of tannaphiles.
B: Materials and Methods
Tannic acid was purchased from different suppliers Sigma Aldrich, Wako pure chemical industries etc. that consists of different isomers of tannic acid. Lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, bromoacetic acid and p-toluenesulfonic acid were purchased from TCI Chemicals. All solvents were purchased from Wako pure chemical industries. NMR solvents were purchased from Sigma Aldrich.
C: Synthetic Process for Synthesis of Various Surface-Active Tannaphiles
(1) Synthesis of Lauryl Ester Tannaphiles (C12 Tannaphiles):
Tannic acid (21.8 g) is dissolved in 100 ml dry dimethylformamide (DMF) by heating at 40 degrees Celsius under inert condition (nitrogen gas atmosphere). The solvent containing dissolved tannic acid is allowed to cool at room temperature. To the stirred solution of tannic acid, dry anhydrous potassium carbonate (11.14 g) is added under inert condition. Further, lauryl 2-bromoacetate (14.74 g) dissolved in 100 ml of dry DMF is slowly added drop wise to the reaction mixture under inert conditions over 150 minutes time frame at 20-25 degrees Celsius. The reaction is further stirred for another 150 minutes (total time 5 hours including addition time). The reaction mixture is then filtered and the DMF is removed by rotary evaporator under reduced pressure/high vacuum. The solid mass thus obtained after removal of DMF is treated with 150ml of ethyl acetate by heating at 40 degrees Celsius for 5 minutes and then filtered to remove ethyl acetate. The solid mass is again dissolved in 100ml ethyl acetate and the process is repeated. The solid mass thus obtained after filtration is dried under reduced pressure in rotary evaporator to get tannic acid based surfactant – C12Tannaphiles.
(2) Synthesis of Myristyl Ester Tannaphiles (C14 Tannaphiles):
Tannic acid (21.8 g) is dissolved in 110 ml dry dimethylformamide (DMF) by heating at 40 degrees Celsius under inert condition (nitrogen gas atmosphere). The solvent containing dissolved tannic acid is allowed to cool at room temperature. To the stirred solution of tannic acid, dry anhydrous potassium carbonate (11.14 g) is added under inert condition. Further, myristyl 2-bromoacetate (16.10 g) dissolved in 110 ml of dry DMF is slowly added drop wise to the reaction mixture under inert conditions over 150 minutes time frame at 20-25 degrees Celsius. The reaction is further stirred for another 150 minutes (total time 5 hours including addition time). The purification is done by following the same procedure described for purification of C12 Tannaphiles.
(3) Synthesis of Cetyl Ester Tannaphiles (C16 Tannaphiles):
Tannic acid (21.8 g) is dissolved in 120 ml dry dimethylformamide (DMF) by heating at 40 degrees Celsius under inert condition (nitrogen gas atmosphere). The solvent containing dissolved tannic acid is allowed to cool at room temperature. To the stirred solution of tannic acid, dry anhydrous potassium carbonate (11.14 g) is added under inert condition. Further, cetyl 2-bromoacetate (17.44 g) dissolved in 120 ml of dry DMF is slowly added drop wise to the reaction mixture under inert conditions over 150 minutes time frame at 20-25 degrees Celsius. The reaction is further stirred for another 150 minutes (total time 5 hours including addition time). The purification is done by following the same procedure described for purification for C12 Tannaphiles.
(4) Synthesis of Stearyl Ester Tannaphiles (C18 Tannaphiles):
Tannic acid (21.8 g) is dissolved in 130 ml dry dimethylformamide (DMF) by heating at 40 degrees Celsius under inert condition (nitrogen gas atmosphere). The solvent containing dissolved tannic acid is allowed to cool at room temperature. To the stirred solution of tannic acid, dry anhydrous potassium carbonate (11.14 g) is added under inert condition. Further, stearyl 2-bromoacetate (18.79 g) dissolved in 130 ml of dry DMF is slowly added drop wise to the reaction mixture under inert conditions over 150 minutes time frame at 20-25 degrees Celsius. The reaction is further stirred for another 150 minutes (total time 5 hours including addition time). The purification is done by following the same procedure described for purification for C12 Tannaphiles.
(5) Synthesis of Oleyl Ester Tannaphiles (C18:1 Tannaphiles):
Tannic acid (21.8 g) is dissolved in 120 ml dry dimethylformamide (DMF) by heating at 40 degrees Celsius under inert condition (nitrogen gas atmosphere). The solvent containing dissolved tannic acid is allowed to cool at room temperature. To the stirred solution of tannic acid, dry anhydrous potassium carbonate (11.14 g) is added under inert condition. Further, oleyl 2-bromoacetate (18.69 g) dissolved in 120 ml of dry DMF is slowly added drop wise to the reaction mixture under inert conditions over 150 minutes time frame at 20-25 degrees Celsius. The reaction is further stirred for another 150 minutes (total time 5 hours including addition time). The purification is done by following the same procedure described for purification for C12 Tannaphiles.
D: Characterization of Tannaphiles by 1D and 2D NMR Spectroscopy
The molecular structure of the Tannaphiles synthesized from tannic acid has been established by both 1D (1H, 13C, 13C APT and 13C DEPT) and 2D (COSY and HETCOR) NMR spectroscopy.
The initial assessment of molecular structure of Tannaphiles is done by 1H proton NMR spectroscopy. Figure 3 shows 1H proton NMR of C12 Tannaphile synthesized from tannic acid consisting of mixture of its isomer.
Individual protons of C12 Tannaphiles are designated based on 2D 1H-1H Homonuclear COSY spectroscopy. The 1H NMR spectral data of C12 Tannaphiles recorded in deuterated solvent mixture of MeOH-d4 (500 μl) and DMSO-d6 (100 μl) shows different sets of proton resonances. The aromatic protons of galloyl moieties were observed downfield in-between δ 6.83 to 7.49 ppm. H-1 of central glucose moiety was observed at δ 6.34 ppm, while H-2 was observed along with H-4 as multiplet at δ 5.65 ppm. H-3 of central glucose moiety was observed at δ 6.00 ppm. The other protons of central glucose moiety (H-4, H-5 and H-6) appear merged with the methylene protons (protons present on either side of ester functional group of hydrophobic alkyl tail) of C12 Tannaphile in between δ 4.07 – 4.61 ppm. The signal at δ 4.80 ppm is because of partially hydrolyzed tannic acid moiety present as isomer. The triplet observed at δ 3.53 ppm is because of hydrolyzed lauryl alcohol present as inseparable impurity with C12 Tannaphile.
Each individual proton signal in 1H NMR spectroscopy can be explained based on the detailed structural analysis of C12 Tannaphiles obtained from 1H-1H Homonuclear COSY analysis of the compound. As expected, the aromatic protons do not demonstrate any correlation peaks in 2D COSY spectra (Figure 4). In contrast the central glucose moiety of C12 Tannaphile demonstrate correlation peaks and H-1, H-2, H-3 and H-4 of the glucose moiety can be easily assigned based on correlation cross peaks observed in 1H-1H Homonuclear COSY spectra (refer to reference 1 and 2). However we have found that the H-5 and H-6 (2H) demonstrate some peculiarities in the observed results which may be due to the inherent nature of these protons since flexibility of the galloyl moiety linked to the C6 methylene group is different compared to other protons whose mobility is restricted by their reciprocal steric hindrance (refer to reference 3). Moreover the sensitivity and chemical shifts of these protons greatly depend on choice of NMR solvents. The methylene protons present in-between galloyl moiety and ester functionality of hydrophobic tail i.e. -OCH2COOCH2- appeared as characteristic singlet among the group of other protons and this proton does not demonstrate any correlation with other protons. The methylene protons of hydrophobic tail adjacent to ester functionality i.e. -OCH2COOCH2-which appeared among the overlapped other proton signal demonstrated cosy cross peak in upfield region. The triplet observed at δ 3.53 ppm is because of hydrolyzed lauryl alcohol also demonstrated correlation peak in the spectra.
Similarly the characterization of other Tannaphiles was done based on 1D and 2D NMR spectra of respective compounds. Figure 5 shows 1H spectra of C14 Tannaphile and C16 Tannaphile.
The molecular structure of the Tannaphiles has been further established by 13C NMR spectroscopy. Each individual type of carbon present in the molecular structure of C12 Tannaphiles can be distinguished by detailed carbon NMR analysis by custom 13C NMR and DEPT analysis. Figure 6 show 13C NMR and DEPT 45 spectra of C12 Tannaphile. The 13C spectrum shows all the carbon associated with the C12 Tannaphiles including the quaternary C=O and solvent carbons. The DEPT 45 spectrum distinguishes quaternary carbon from other carbons i.e. CH, CH2 and CH3 as signal for quaternary carbon is not observed in DEPT. There is slight upfield chemical shift of reference solvent peak as mixed deuterated solvent system is used for evaluating C12 Tannaphiles. Dimethylsulfoxide-d6 and methanol-d4 appeared as septet at δ 37.1 and 46.5 ppm respectively. These signal were not visible in DEPT spectra as the carbon of solvents are bonded to deuterium and not protons.
The characteristic peak for the methylene carbon -OCH2COOCH2- which is also the source peak for the point of attachment of tannic acid with hydrophobic tail appeared at δ 71.2 ppm in all the spectrum. The position of this peak is also confirmed from 2D 1H-13C HETCOR. The characteristic peak for the aromatic CH carbon of the galloyl moiety appeared in-between δ 107.5-108.2 ppm. The other quaternary carbon of aromatic ring and carbonyl groups are not observed in DEPT spectrum however they are evident in 13C spectrum. The signal for traces of lauryl alcohol that is associated with C12 Tannaphiles is also visible in 13C NMR spectra at δ 60.3 ppm. The signal for central glucose moiety of the C12 Tannaphiles are visible between δ 63.3-69.4 ppm however the signal intensities of these signal are less compared to other carbon signals. This may be due to mobility restriction due to steric hindrance.
E: Self-aggregation properties of C12 Tannaphile investigated by Surface Tension Measurements (see Fig. 7)
The self-aggregation properties of Tannaphiles have been investigated by surface tension measurements. Figure 7 shows plot of surface tension versus log of concentration plot of C12 Tannaphile.
The critical micelle concentration of C12 Tannaphile is determined by surface tension measurements.
C12 Tannphile demonstrated ability to form micelle at very low surfactant concentration. The cmc value of C12 Tannphile is 0.0102 wt.% (102 mg per liter) in aqueous solution. The affinity to reduce surface tension at cmc (gamma cmc) is 33.1 mNm-1. The evaluated cmc value of C12 Tannaphile is much lower compared to commercially available anioic surfactants like sodium dodecyl sulfate (SDS), sodium lauryl sulfoacetate (SLSA) and alkylbenzenesulfonate (BAS) surfactants. The C12 Tannphile also demonstrates excellent foaming ability at very low surfactant concentration of 0.02 wt.% (above its cmc value).
F: Intra/Intermicellar Interactions of Tannaphile Micelles in Aqueous Solution (see Fig. 8)
Tannaphile micelles demonstrate unique ability to interact in aqueous solution by:
(i) π-π interaction
(ii) Ion-π interaction
(iii) Hydrogen Bonding
Intra/Intermicellar interaction of Tannaphile micelles is investigated by:
(i) Dynamic Light Scattering Measurements
(ii) Zeta Potential Experiments
(iii) NMR Experiments
G: Tannaphile Micelle Size Investigation in Aqueous Solution by Dynamic Light Scattering Technique (see Fig. 9)
We have intensity weight mode, number weight mode, and volume weight mode at different surfactant concentration.
Hydrodynamic radius of the micelles formed by C12 Tannaphile is determined by dynamic light scattering technique. Figure 9 shows the size distribution of micelles formed by the C12 Tannaphile for different surfactant concentration determined at 25 degrees Celsius. The results indicate that the aggregates with different sizes and morphologies are formed depending on surfactant concentration. Two merged broad peaks are observed for the micellar solution of C12 Tannaphile at different surfactant concentrations (i.e. 0.25 wt.%, 0.50 wt.%, 1.00 wt.% and 2.00 wt.% in water).
The average hydrodynamic radius varies from 34 to 58 nm depending on surfactant concentration. The observed results indicate that the C12 Tannaphile are able to form different structural morphologies by intra/inter-miceller interactions by varying the concentration. At higher surfactant concentrations above the critical micelle concentration, the intra/inter micellar interactions modify the free diffusion of micelles and this leads to non-specific aggregation that modifies the observed size distribution. The intra and inter micellar interactions is evident by the observed results investigated by Zeta Potential Experiments and NMR experiments (discussed later).
H: Zeta Potential Distribution of C12 Tannaphile in Water at Different Concentration (see Fig. 10)
ζ-Potential measurements of C12 Tannaphile in water at different surfactant concentration were conducted on Anton Paar Litesizer 500 instrument.
The surface of Tannaphile micelles are negatively charged and hence positively charged potassium ion builds around the surface of micelle forming electric double layer.
In all cases, the ζ-Potential peaks exhibit broadening probably due to the presence intra/intermicellar interaction of C12 Tannaphile micelles as a result of π-π interaction between the galloyl moieties of headgroup, ion-π interaction between charged ions and galloyl moiety, hydrogen-π interaction, and hydrogen bonding between polar functional groups present within molecules as well as between polar functional groups and water molecules. These type of non-covalent interactions significantly alters observed zeta potential with change in Tannaphile concentration in water. The ζ-potential is often used as an index of the magnitude of electrostatic interaction between colloidal particles and is thus a measure of the colloidal stability of the solution. Micelles with a ζ-potential less than -15 mV or more than 15 mV are expected to be stable from electrostatic considerations. It has been found in our studies that upon increasing the concentration of C12 Tannaphiles in aqueous solution the absolute ζ-potential values drastically changes. The ζ-potential distributions observed here are probably due to strong intra/intermicellar interaction of C12 Tannaphile micelles by non-covalent interactions such as π-π interaction between the galloyl moieties of headgroup, ion-π interaction between charged ions and galloyl moiety, hydrogen-π interaction, and hydrogen bonding between polar functional groups present within molecules as well as between polar functional groups and water molecules. Such interactions significantly alter the shape, size and ζ-potential distributions of micelles. This has been investigated in detail by NMR spectroscopy discussed in next section.
I: NMR Investigation of Micellar Solution of C12 Tannaphile at Different Concentration (see Fig. 11)
The C12 Tannaphile was further investigated by proton NMR spectroscopy to study the nature of interaction exhibited by the Tannaphile in the solution phase. Different concentration of C12 Tannaphile was investigated in polar D2O and CD3OD mixed solvent system. Figure 11 shows proton NMR spectra of C12 Tannaphile at different concentration.
It is evident from the results of the NMR spectroscopy that the micelles of the Tannaphile in aqueous solution demonstrates ability to interact via non-covalent inter and intra miceller interactions. The observed proton signals in aromatic region as well as non-aromatic region shows significant changes upon increasing the concentration in deuterated solvent system. The changes occurring in the aromatic region between δ 6.8 to 7.5 ppm is primarily due to:
1) π-π interaction between the galloyl moieties of headgroup
2) Ion-π interaction between charged ions and galloyl moiety and
3) Hydrogen-π interaction between the protons adjacent to ester functionality and galloyl moieties of headgroup
All these non-covalent interactions significantly alter the observed resonance of proton signals in aromatic region, which is visible in figure 11. Similarly the some of the methylene protons as well as methine proton (as shown in figure 11 on right hand side) demonstrates change in resonance. This is attributed to strong hydrogen-π interaction.
Apart from these kind of non-covalent interactions mentioned above, hydrogen bonding between the -OH protons of galloyl moiety and water molecules also play important role in influencing the observed characteristic properties of the system.
As showing one model in figure 12, methylene protons (e,d and 6) and methine proton (5) demonstrate significant downfield chemical shift along with significant change in observed NMR signal due to inter micellar hydrogen bonding (see ig. 12).
The dispersing composition, the method of dispersing crude oil emulsion, the method of dispersing asphaltene contained in crude oil and the method of s dispersing asphaltene contained in asphalt cement of the present invention are described bellow.
Dispersing composition:
In accordance with the present invention, the dispersing composition is comprising of containing the tannic acid based surface-active compounds Tannaphile in a solution like aqueous. The dispersing composition may be made as the Dilute Aqueous Solution of Tannaphile.
A: Viscosity Measurements of the Dilute Aqueous Solution of Tannaphile (see Fig. 13)
The viscosities of the micellar solution of C12 Tannaphile were investigated by rheometer for different concentrations at 25degrees Celsius. The aqueous micellar solution of C12 Tannaphile demonstrated Newtonian fluid behavior between 0.25-2.00 wt.% since the observed viscosities are independent of the applied shear rate. Figure 13 shows viscosity (η) vs. shear-rate (γ) plot for the aqueous micellar solution of the C12 Tannaphile surfactants at 25degrees Celsius for various concentrations from 0.25wt.% to 2.00wt.%.
The aqueous micellar solution of Tannaphile demonstrated Newtonian fluid behavior as the observed viscosities are independent of the applied shear rate.
Some methods of using the dispersing composition will be described below.
Method of dispersing crude oil emulsion:
In accordance with the present invention, the method of dispersing crude oil emulsion is comprising of putting crude oil emulsion into the above-mentioned dispersing solution then vibrating or mixing the dispersing solution and the crude oil emulsion to disperse the crude oil emulsion into the dispersing solution.
Tannaphile has demonstrated promising capability to solubilize crude oil in aqueous system and hence can be used for Enhanced Oil Recovery Application. Crude oil is stable emulsion of oil fractions-asphaltene-petroleum waxes of high viscosity and hence very difficult to extract out of petroleum reservoir.
Often treatment with some selective chemicals affords enhanced oil recovery.
Tannaphile is very effective in solubilizing oils by using it in accordance with the method of dispersing crude oil emulsion of present invention.
Since crude oil is stable emulsion oil, asphaltene and waxes along with traces of some metal impurities. It is very viscous and difficult to extract from petroleum reservoir.
Example 1:
For instant result we have used 2wt.% Tannaphile solution as a dispersing solution of present invention.
Treatment with dilute solution (0.25-0.5%) requires incubation time of 5-10 minutes before crude oil starts solubilizing in aqueous Tannaphile solution.
After 5-10 minutes from the start of vibrating or mixing, the crude oil emulsion has dispersed finely into the dispersing solution.
Example 2:
Tannaphile Based Dispersing Agent for Cleanup of Oil Spills by following steps.
Step 1: Spraying Tannaphile based oil dispersing agent on the oil spills area in the sea, lakes, rivers and so on.
Step 2: Tannaphile can break oil into small droplets.
Step 3: Small dispersed oil droplets may be more readily biodegraded by microbes.
Step 4: Tannaphiles can be easily degraded due to its biocompatible nature offering complete cleanup of organic residue.
Oil spill is the release crude or processed hydrocarbon into marine ecosystem which causes great harm to environment and ecosystem. We intend to use this new sustainable molecule as oil dispersing agent to deal with Oil spill problem. The present invention can solve these Oil spill problem easily.
Example 3:
Tannaphile Based Dispersing Agent for Sending out Crude Oil Component from the Crude Oil Layer by following steps.
Step 1: Injecting Tannaphile based oil dispersing agent with high pressure into a crude oil layer underground,
Step 2: Dispersing a crude oil component of the crude oil layer into the dispersing solution.
Step 3: Sending out the dispersing solution and the crude oil component from the crude oil layer.
Since Tannaphile can disperse crude oil into fine droplets in water it can be effectively used as oil dispersing agent and deal with the oil spill problem and difficulty of sending out crude oil component. Also since Tannaphile is based on natural structural design it will be better than several synthetic dispersing agent currently being used.
Method of dispersing asphaltene contained in crude oil:
In accordance with the present invention, the method of dispersing asphaltene contained in crude oil is comprising putting crude oil emulsion into the dispersing solution containing the above-mentioned dispersing composition and vibrating or mixing the dispersing solution and the crude oil emulsion to disperse the asphaltene from the crude oil emulsion.
Example 1:
Tannaphile Based Dispersing Agent for Dispersing Asphaltene contained in Crude Oil by following steps.
Step 1: Putting crude oil emulsion into Tannaphile based oil dispersing agent.
Step 2: Vibrating or mixing the Tannaphile based oil dispersing agent and the crude oil emulsion.
Step 3: Dispersing the asphaltene from the crude oil emulsion.
The present invention can disperse the asphaltene from the crude oil emulsion easily.
Method of dispersing asphaltene contained in asphalt cement:
In accordance with the present invention, the method of dispersing asphaltene contained in asphalt cement is comprising contacting the dispersing solution containing the dispersing composition according to claim 4 and asphalt cement and vibrating or mixing the dispersing solution and the asphalt cement together with heating them to disperse the asphaltene from the asphalt cement.
Example 1:
Tannaphile Based Dispersing Agent for Dispersing Asphaltene contained in Asphalt Cement by following steps.
Step 1: Contacting the Tannaphile based oil dispersing agent and asphalt cement.
Step 2: Vibrating or mixing Tannaphile based oil dispersing agent and the asphalt cement together with heating them.
Step 3: Dispersing the asphaltene from the asphalt cement.
The present invention can disperse the asphaltene from the asphalt cement easily.

Claims (4)

  1. Tannic acid based surface-active compounds comprising one of the following chemical schemes (1) to (5).
    Figure JPOXMLDOC01-appb-I000001
  2. Tannic acid based surface-active compounds comprising of a hydrophobic group of tannic acid and a hydrophibic group of aliphatic alcohol.
    The aliphatic alcohol has C12, C14, C16 or C18.
  3. A method of producing tannic acid based surface-active compounds, comprising,
    synthesizing plant-based tannic acid and aliphatic alcohol and
    filtering the synthesized material to obtain tannic acid based surface-active compounds.
  4. A dispersing composition comprising of containing the tannic acid based surface-active compounds in accordance with claim 1 or claim2.
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CN111320728B (en) * 2020-03-20 2022-06-21 陕西科技大学 Amphoteric tannin-based coal tar pitch water slurry dispersing agent and preparation method thereof

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