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Pure and Applied Chemistry
ISSN: 1060-1325 (Print) 1520-5738 (Online) Journal homepage: https://www.tandfonline.com/loi/lmsa20
Novel Water Soluble Soya Oil Polymer from
Oxidized Soya Oil Polymer and Diethanol Amine
Merve Acar , Selim Çoban & Baki Hazer
To cite this article: Merve Acar , Selim Çoban & Baki Hazer (2013) Novel Water Soluble Soya Oil Polymer from Oxidized Soya Oil Polymer and Diethanol Amine, Journal of Macromolecular Science, Part A, 50:3, 287-296, DOI: 10.1080/10601325.2013.755443
To link to this article: https://doi.org/10.1080/10601325.2013.755443
Published online: 01 Feb 2013.
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Journal of Macromolecular Science, Part A: Pure and Applied Chemistry (2013) 50, 287–296
CopyrightCTaylor & Francis Group, LLC ISSN: 1060-1325 print / 1520-5738 online DOI: 10.1080/10601325.2013.755443
Novel Water Soluble Soya Oil Polymer from Oxidized
Soya Oil Polymer and Diethanol Amine
MERVE ACAR, SEL˙IM C¸ OBAN, and BAK˙I HAZER∗
B¨ulent Ecevit University, Department of Chemistry, Zonguldak, Turkey Received, Accepted September 2012
A cold water soluble, biobased polymer derived from autoxidized soya oil has been described. Oxidized soya oil polymer was obtained by exposure to air under daylight at room temperature. The thickness of the soya oil at the beginning of the reaction and the oxidation time adversely influenced the molecular weight of the soya oil polymer obtained. The oxidized soya oil polymer obtained was then reacted with diethanol amine to obtain a hydroxylated soya oil polymer. The cold water soluble hydroxylated soya oil polymer was characterized by viscosity measurements, elemental analysis, FT-IR,1H-NMR,13C-NMR and cosy-NMR.
Keyword: Water soluble polymer, autoxidation, soya oil, diethanol amine, hydroxylated soya oil polymer
1 Introduction
Monomers from renewable resources, such as soybean oil, have gained special attention to prepare polymers because of environmental concerns and the depletion of the world’s petroleum pool (1, 2). Soya oil is one of the most abun-dant and inexpensive renewable sources in order to pre-pare high molecular weight polymers and is composed of poly-unsaturated fatty acids with the main component be-ing linoleic acid (ca. 50 wt%) (3–8). Hydroxylated soya oils are important for the preparation of the waterborne polyurethanes in aqueous dispersions which are widely used for applications such as adhesives and coatings of various materials, e.g., textiles, metals, plastics, and wood (9–11). Hydroxylated soya oils can be obtained in several ways for the preparation of polyurethane materials (12): (i) Ring opening reactions of epoxidized soya oil by using catalytic hydrogenation, hydrochloric or hydrobromic acid, acidified methanol and water (13), and ethylene glycol and 1,2 propane diol (14); (ii) Concentrated phosphoric acid in chloroform can be used to open epoxide group lead-ing to hydroxylation (15); (iii) Hydroxylated soya oil can be obtained by reacting formic acid and hydrogen perox-ide with soya oil. A one-pot reaction with H2O2/HCOOH
∗Address correspondence to: Baki Hazer, B ¨ulent Ecevit
Uni-versity, Department of Chemistry, 67100 Zonguldak, Turkey. Tel: 0372 2574010-1372; Fax: 0372 2574181; Email: bkhazer@ karaelmas.edu.tr, bhazer2@yahoo.com
or CH3COOH, resulting in a fully formiated soy polyol
(16); (iv) Ozonolysis and hydrogenation based technol-ogy can be used to prepare a soya oil based polyol (17); (v) The amidation of a plant oil with diethanolamine, using sodium methoxide as a catalyst, produces a diol fatty amide (18); (vi) Hydroformylation (CO, H2, catalyst)/reduction
(H2, catalyst Ni) of the double bonds of unsaturated fatty
acid gives a polyol (19); (vii) Autoxidation of polyunsat-urated oils affords polymeric oil peroxides via hydrogen abstraction from a methylene group between two double bonds. Autoxidation gives hydroperoxides as the intial or primary oxidation products. Subsequent breakdown of the hydroperoxides, depending upon the conditions gives sec-ondary products such as aldehydes, ketones, epoxides and cyclic peroxides that undergo reaction and produce poly-merization products (20–24). After the autoxidation pro-cess, the whole mass of soya oil transforms to the sticky, waxy soya oil polymer.
In our polymer research laboratories, because of their peroxide inclusion as a free radical source, autoxidized poly unsaturated oils/fatty acids were first used as a macroperoxyinitiator in free radical copolymerization of some acrylic polymers to obtain graft copolymers (22). Soybean oil can also be polymerized by autoxidation under air oxygen and sunlight via peroxidation, epoxidation and perepoxidation (23). The soya oil polymer peroxide can be converted to a polyol by using an Fe (III) catalyst. In that case, the hydroxylated soya oil polymer is swellable in water and it contains some iron catalyst residue (25). This work refers to the preparation of a novel wholly water soluble
soya oil polymer from the autoxidized soya oil polymeric peroxide and diethanol amine. For this purpose, polymeric soya oil peroxide was obtained by the autoxidation with air oxygen. The dependence of the molecular weight of soya oil polymer and the autoxidation time were also studied in view of the autoxidation kinetics. The soya oil thick-ness at the beginning of the autoxidation was evaluated by means of the autoxidation kinetics. In the second part of this work, soya oil polymer peroxide was reacted with di-ethanol amine to obtain a cold water soluble hydroxylated soya oil polymer.
2 Experimental
2.1 Materials
Soya oil was a gift from C¸ otanak/Altas¸ Ya˘g Su ve Tarım ¨Ur ¨unleri Gıda ˙Ins¸aat Otomotiv Nakliyat San. ve Tic.A.S¸. Ordu, Turkey. It contains palmitic acid (10.7 wt%), stearic acid (4.6 wt%), oleic acid (23.5 wt%), linoleic acid (52.8 wt%) and linolenic acid (5.7 wt%). Antioxi-dant adduct inside the commercial soya oil was removed by leaching with ethanol three times. Diethanol amine, and other chemicals and the solvents were supplied from Aldrich and used without further purification.
2.2 Formation of Polymeric Soybean Oil (PSy-ox) under Laboratory Conditions
Autoxidation of soya oil was performed according to the modified procedure reported in our previous work (25). For example, 2.7 g of soya oil spread out in a Petri dish (F= 7 cm, oil thickness: 0.7 mm) was exposed to daylight in the air at room temperature.
Oil thickness in Petri dish was calculated by the following Equation 1:
h= V/πr2 (1)
Where V= m/d, m is the mass of soya oil (g) in Petri dish, d and V are the density (approx. 0.9 g/cm3), and volume
(cm3) of the soya oil in Petri dish, respectively, r is the radius
(cm) of the Petri dish, and h (cm) is the oil thickness. After a given time of autoxidation, a waxy, viscous poly-mer film was formed with a yield 85–90 wt%.
2.3 Hydroxylation Reactions of Soya Oil Polymer
Hydroxylation reaction of PSy-ox and diethanol amine was performed in a round bottom flask at 90◦C for 24 h. As an example, a round bottom flask (250 mL) containing 5.0 g of PSy-ox and 5.0 mL of diethanol amine were kept in an oil bath at 90◦C for a day. The crude product was dissolved in 20 mL of acetone. It was filtered and then
the hydroxylated soya oil polymer was precipitated into 100 mL of petroleum ether. The hydroxylated soya polymer was dried under vacuum at room temperature for 24 h. Water solubility was tested in a test tube by mixing the hydroxylated soya polymer (ca. 0.6 g) with distilled water (ca. 5 mL). For solubility test in acidic solution, 0.1 N HCl was used instead of distilled water.
2.4 Thermal Decomposition of the Oxidized Soya Oil Polymer
Thermal decomposition of the soya oil polymer was car-ried out as follows: 5.0 g of PSy-ox in a round bottom flask was kept in oil bath at 90◦C for a day. The change in molecular weight of the cured polymer was measured using viscometry.
2.5 Viscosity Measurement
For this purpose, a series of the soya polymer solutions 1.0, 0.80, 0.64, 0.39, 0.24 (g/100 mL CHCl3) were prepared.
Flow times of these solutions and the solvent were deter-mined by using an Ubbelohde viscometer at 25◦C. Then intrinsic viscosity, [η], expressed in deciliters per gram, was determined by using a plot of specific viscosity, [η]sp, vs. solution concentrations of the soya polymer. [η]spis calcu-lated from the following Equation 2:
[η]sp= [(t − to)/to]/c (2)
Where t is flow time of the solution, to is flow time of
the solvent, and c is the solution concentration as g/dL. Extrapolation of the linear plot of [η]spvs. c to zero c, gives the intrinsic viscosity, [η] (26).
Equation3 describes the dependence of the intrinsic vis-cosity of a polymer on its molecular weight and having the form:
[η]K · Mna (3)
Where [η] is the intrinsic viscosity, K and a are constants and Mn is the relative molecular mass averages (ca. Number average molecular weight measured by using GPC).
2.6 Instrumentation 2.6.1 NMR
The 1H NMR, 13C NMR and cosy-NMR spectra of the
polymers were recorded on a Bruker AVANCE 400 spec-trometer (400 MHz) using CDCl3as the solvent.
2.6.2 FTIR
FTIR and FTIR-ATR (attenuated total reflectance spec-troscopy) spectra were recorded using a Nicolet 520 model FTIR Fourier Transform Infrared Spectrometer and
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Perkin-Elmer FTIR Spectrometer 100. The FTIR spectra of the graft copolymers were taken as KBr samples.
2.6.3 Elemental Analysis
The CHNS-932 Model LECO Elemental Analyzer was used for the elemental analysis of C and H in the soya oil products.
2.6.4 Gel Permeation Chromatography (GPC)
GPC measurements of the polymer samples in tetrahy-drofuran (THF) solutions were carried out by using a Polymer Laboratories Gel Permeation Chromatography (GPC) instrument Viscotek GPCmax Autosampler sys-tem, consisting of a pump, three ViscoGEL GPC columns (G2000HHR, G3000HHR, and G4000HHR), a Viscotek UV detector, and a Viscotek differential refractive index detector with a THF flow rate of 1.0 mL min−1 at 30◦C. Both detectors were calibrated with PS standards having narrow molecular weight distribution. Data were analyzed using Viscotek OmniSEC Omni–01 software.
3 Results and Discussion
Poly unsaturated oils such as sesame, linseed and soya oils are drying oils. It has been known for a century that they are polymerized via air oxygen leading to polymeric oil per-oxides when these oils are exposed to air under daylight at room temperature. Another industrial way to autoxidized drying oils is passing air or oxygen into the oil at 75–90◦C which is called “blown oil” (27–29). Drier catalysts such as the salts of lead, manganese, and cobalt are used extensively in blown oil process (28). The autoxidation mechanism at room temperature is related to the formation of epoxide, peroxide and hydroperoxide groups. So, our research group used the oxidized oil polymers as a macroperoxidic initia-tor in order to initiate free radical polymerization of methyl methacrylate, n-butyl methacrylate, and N-isopropyl acryl amide (21–24). The initiation event of the autoxidation pro-cess is the removal of bisallylic hydrogen to form a carbon-centered radical with electron density at the central carbon and the two termini. Autoxidation steps and mechanisms in detail have been given in cited fine review article published by Soucek et al., very recently (30). During this study, we obtained at least 6 autoxidized soya oil polymers for kinetic study and 3 ones for the hydroxylation reactions. Totally 9 oxidized soya oil polymer samples were prepared.
Oxygen trapping of the carbon-centered radicals pro-duces peroxyl radicals, which react with another molecule of fatty acid to produce hydroperoxide products and an-other carbon-centered radical. This represents the prop-agation step, which enables the continuation of the free radical chain reaction leading to soya oil polymer.
3.1 Effect of Soya Oil Thickness and Oxidation Time on the Molecular Weight of the Soya Oil Polymer As far as we know, autoxidation kinetic under atmospheric conditions in view of the oil thickness and the autoxida-tion time was not studied until now. Therefore, we first performed the kinetic study in the present work. Secondly, the autoxidized soya oil polymer sample were reacted with diethanol amine to obtain first a novel wholly water soluble hydroxylated soya oil polymer. For the kinetic study, soya bean oil was autoxidized under atmospheric conditions at room temperature without using any inorganic catalyst and any heating process, by means of environmentally friendly chemistry process. For the kinetic study of the soya oil au-toxidation, six different Petri dishes containing different amount of soya oil inside were used. Oil thickness of soya oil was calculated by using Equation 1. Then, six series of the soya oil with different oil thickness (mm): 0.7, 1.0, 1.4, 1.7, 2.1, and 2.9 (not listed in a Table) in Petri dishes was exposed to air for the 21, 40 and 69 day intervals. After-wards, intrinsic viscosities of the oxidized soya oil polymer samples were determined after the oxidation time intervals to have plots of oil thickness versus intrinsic viscosities for different oxidation time intervals. Figure 1 presents the ox-idation kinetics obtained the data from the variation of the viscosity of the soya oil polymer with the soya oil layer thickness and the autoxidation time. First, we roughly ob-tained lines related to three different data group showing the decrease viscosity value with increasing the layer thick-ness. A second point is that there is an increase in viscosity value of the oil polymer formed with the increasing oxi-dation time. For example, in Figure 1, it is observed that
Fig. 1. Variation of the intrinsic viscosities of the soya oil polymers
with different oil thickness in Petri dish. Autoxidation time: 21 days, 40 days, 69 days. (Color figure available online.)
Table 1. Results and conditions of the autoxidized soya oil polymers
GPC Results Elm. Analysis, (wt%) Oil thickness, Oxidation
Code (mm) time, (day) η, (dL/g) Mn×104 Mw×104 MWD C H O
Soya oil — 0 0.13 76.8 11.13 12.1
PSy-1 0.5 35 0.35 12.6 20.6 1.63 67.3 9.18 23.6 PSy-2 1.0 90 0.28 4.46 8.54 1.93 70.5 9.77 19.7 PSy-85 3.0 90 0.17 2.26 4.73 2.09 70.3 9.72 20.0
longer autoxidation time increases the molecular weight of the soya oil polymer, where at a constant layer thickness of 0.7 mm at oxidation times of 21, 40 and 69 days, the vis-cosities of the soya oil polymer are 0.136, 0.222, and 0.283 dL/g, respectively. It is worth to say that no crosslinked polymer is formed during the autoxidation process.
A series of autoxidized soya oil polymer samples in Petri dishes with the thickness of oil changing from 0.5 mm to 3.0 mm were obtained and coded 1, 2 and PSy-85. Intrinsic viscosities ([η]), GPC results, oxidation time and the C and H elemental analysis results are tabulated in Table 1. Total captured oxygen amount during autoxi-dation was calculated from the elemental analysis results tabulated in Table 1. Autoxidized soya oil polymer con-tained oxygen in range between from 19.7 to 23. 6 wt% while that of the piristine soya oil was 12.1 wt%. There is a good agreement of oxygen content in autoxidized soya oil polymer with that of the blown oil reported in the cited ref-erence (28). Approximately, an additional 10 wt% of oxygen was introduced into the oxidized soya oil polymer. This is roughly equivalent to six oxygen atoms per soya polymer repeating unit coming from peroxide, hydroperoxide and epoxide groups. In case of the thinnest oil thickness, the highest amount of oxygen was trapped in the autoxidized soya oil polymer in the shortest autoxidation time. Table 1 also indicates that longer oxidation times and less oil thick-ness cause higher molecular weight of the soya oil polymer, as we expected. This soya oil polymer obtained from the thinnest oil thickness also had the highest intrinsic viscos-ity. Mn, Mw and molecular weight distribution (MWD) of the autoxidized soya oil polymers PSy-1, -2 and -85 are listed in Table 1.
As we expected, the soya oil polymer (PSy-1) obtained from the thinnest soya oil in the Petri dish had the highest Mn: 126000 while the others were 4400 and 2200 g/mol. In addition to this, GPC chromatogram of PSy-1 was uni-modal, while those of the soya oil polymers obtained from the thicker soya oil in Petri dish were multimodals. Figure 2 shows the GPC chromatograms of the soya oil polymers, PSy-1, -2 and -85. The molecular weight distribution also increased as the oil thickness in Petri dish increases. This shows that the oil surface layer is oxidized much faster than the oil layer inside as expected. In the beginning of the ox-idation of soya oil, polymerization improves slowly, the oil
surface probably is oxidized first and then the oxidation improves inside the oil layer.
Additionally, an oxidized soya oil polymer obtained from the soya oil with 0.5 mm layer thickness was a mixture of gelled and soluble polymer. It contained the 30 wt% of gel polymer. However, it was used without fractionation of the gel polymer before hydroxylation reactions.
3.2 Hydroxylated Soya Oil Polymers
After the autoxidation process the whole mass of soya oil transformed to a sticky, waxy soya oil polymer which was used for hydroxylation reaction without extraction. We have very recently transformed the oxidized soya polymer to the hydroxylated soya polymer by using iron (III) catalyst which is swellable in water (25). Soya oil polymer was hy-droxylated by this way but not soluble in water. In this work, we have used diethanol amine to prepare wholly cold water soluble soya oil polymer. Oxidized soya oil polymer was reacted with diethanol amine to obtain hydroxylated soya
Fig. 2. GPC chromatograms of the autoxidized soya oil polymers
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Table 2. Hydroxylation of the oxidized soya polymers by using diethanol amineGPC Results Analysis (wt%) Code Sy-1, (g) Sy-2 (g) DEA, (mL) Yield, (g) Mn×104 Mw×104 MWD C H N O
NSy-1 5.0 — 5.0 3.0 0.59 0.88 1.48 50.1 9.62 5.66 34.62 NSy-2 — 5.0 5.0 3.0 0.38 0.57 1.52 53.8 9.71 5.13 31.46
oil polymer (PSy-OH). Epoxide, peroxide and ester groups of autoxidized soya oil polymer were simply converted to hydroxyl groups by the reaction with diethanol amine. We obtained at least 6 water soluble hydroxylated samples but only three of them were inserted into the Table 2. Reaction conditions and the results of the hydroxylation reactions were tabulated in Table 2.
Scheme 1 shows the representative chemical structure of soybean oil, oxidized soybean oil, and the hydroxylation re-actions. When the epoxide group is converted to a hydroxyl moity, the diethanol amine residue is attached to the soya polymer (Sch. 1 (a)).
Diethanol amine also produces hydroxyl groups by the reaction of peroxide groups (Sch.1 (b)). In this case, an alkoxy amine is induced during the reaction and then it has a tendency to decompose into an alcohol and a Schiff base. In the third reaction of an amine with oxidized triglyc-eride, the amidation reaction of diethanol amine with ester groups was carried out (Sch. 1 (c)). As we will discuss in the following paragraphs related to the spectrometric
anal-ysis of the hydroxylated samples, amidation reactions were carried out between diethanol amine and the triglyceride.
3.3 Spectrometric Characterization
The functional groups of soya oil polymers were first con-firmed by FTIR. Figure 3(a) shows the FTIR spectrum of pure soya oil with the characteristic signals to compare with that of the functionalized soya oil polymers.
FTIR spectrum of autoxidized soya oil polymer in Fig-ure 3(b) has additional bands at 3400 cm−1 (hydroperox-ide groups) and at 810 cm−1(epoxide group). The FTIR spectrum of hydroxylated soya oil polymer using diethanol amine contains new bands at 3300 cm−1(alcohol groups), at 1615 cm−1 (amide carbonyl group) and at 1046 cm−1 (C-O bands) while the ester carbonyl band at 1742 cm−1 and original C-O bands at 1160 cm−1and 1097 cm−1 dis-appeared (Fig. 3c).
In order to evaluate the chemical structure of the func-tionalized soya oil polymers, 1H-NMR, 13C-NMR and
Fig. 3. FTIR spectra of the functionalized soya oil polymers: (a) pure soya oil, (b) PSy-ox (PSy2), (c) hydroxylated soya oil polymer
Sch. 1. (a). Soybean oil. (b). Representative chemical structure of the soybean oil polymer obtained by autoxidation of soybean oil.
(c). Hydroxylated water soluble soybean oil polymer.
cosy-NMR were also used in the spectrometric characteri-zation. Figure 4 shows the1H NMR spectra of the oxidized
soya oil polymer (a) and hydroxylated soya oil polymer by DEA (b).1H-NMR spectrum of oxidized soya oil polymer
in Figure 4 (I) has the characteristic signals same as those of the pure soya oil (31): d(ppm): 5.4 ( CH CH ), 4.1–4.2
(doublet, CH2O(OC ) CHO(OC ) CH2O(OC ), 2.7
( CH CH CH2 CH CH ), 2.3 ( CH2 COO ),2.0
( CH2 CH2 CH CH ), 1.6 ( CH2 CH2 COO ),
1.3 (CH2) n,0.9 [CH3 (CH2) n].In the1H-NMR
spec-tra of the hydrolyzed soya oil polymer obtained by us-ing diethanol amine (Fig. 4 II) new bands (32–34) ap-peared at 4.1 (–N CH2 CH2 OH), 3.5–3.8 ( C O , C OH induced) and 2.7 ( N CH2 CH2 OH)
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Fig. 4.1H-NMR spectra of the hydroxylated soya oil polymers: (I) autoxidized soya oil polymer (Sy-2), (II) hydroxylated soya oil polymer obtained from diethanol amine (NSy-2).
while disappeared the band at 4.1–4.2 (doublet, CH2O(OC ) CHO(OC ) CH2O(OC ) which con-firmed again the transamidation reactions occur during the hydroxylation reactions induced by the diethanol amine.
13C-NMR spectra of the hydroxylated soya polymer
sam-ples confirmed their chemical structures. Table 3 contains the13C-NMR chemical shifts of the polymer samples.
The chemical structure of the hydroxylated soya oil poly-mer obtained by diethanol amine was also confirmed by using two-dimensional NMR (Fig. 5). The NMR spectra indicated dihydroxyl sites at d (ppm) 3.1–4.1 coupled each
other in cosy-NMR.
Figure 6 shows the GPC curves of the cold water sol-uble polymer samples, NSy-1 and NSy-2. Hydroxylation reaction causes partially degradation of the oxidized soya oil polymer and leads to lower molecular weight with a smooth, unimodal GPC curve (Fig. 6). The Mn’s of the soya oil polymer decreased after hydroxylation, for exam-ple Mn of hydroxylated PSy-1(NSy-1) decreased to 5900 from 126000 g/mol. Furthermore, cross-linked soya oil
polymer part was also solubilized by the reaction of di-ethanol amine. For the other hydroxylated sample, NSy-2, Mn decreased to 3800 from 4460 g/mol with unimodal GPC chromatograms.
3.4 Elemental Analysis of the Hydroxylated Soya oil Polymer
Results of the elemental analysis of the hydroxylated soya oil polymers also confirmed that diethanol amine was in-troduced into the soya oil polymer. Table 2 contains the per-centage of the C, H, N, and O in the hydroxylated soya oil polymers (NSy-1 and NSy-2). The increase of 11–14 wt% of oxygen was observed after diethanol amine was reacted with soya oil polymer. If we take the molecular weight of soya oil 900 g/mol, in average, each repeating unit of triglyc-eride contains 4 nitrogen atoms according to the N analysis. The increase in oxygen amount is also equal 8 oxygen atoms coming from additional diethanol amine attached to soya
Table 3.13C-NMR chemical shifts (ppm) of the oxidized soya oil polymer (Sy-2), hydroxylated soya oil polymer obtained by using diethanol amine (NSy-2)
Sample Code Chemical shift, (dppm)
Sy-2 173 129, 127 69, 62, 33, 31, 29, 27, 25, 24, 22, 13 NSy-2 176 130, 128 87, 73, 66, 64, 62, 58, 57, 53, 51, 43, 34, 32, 30, 28, 25, 22, 13
Fig. 5. Cosy-NMR spectrum of the hydroxylated soya oil polymer obtained by using diethanol amine (NSy2). (Color figure available
online.)
oil polymer. So, we can conclude that each repeating unit of soya oil polymers contains 4 diethanol amine molecules attached. We can simply calculate the number of oxygen (#O) and nitrogen atoms (#N) in repeating units of the soya oil polymer, by using the following equations:
#O= (O, wt%) × 900 : 16; #N = (N, wt%) × 900 : 14 3.5 Water Solubility
The water solubility of the hydroxylated soya oil polymer samples was examined. For this purpose, 0.65 g of NSy-1 was weighed into a bottle, and then 6 mL of distilled water was added to this sample. It gave a clear solution when shaken manually. But 1M HCl was precipitated the hydroxylated soya oil polymer. Figure 7 shows the PSy-ox samples with all the pale yellow colors, hydroxylated soya oil polymer (NSy-1) and the neutral aqueous solution of NSy-1 with dark brown color. Interestingly, because of the different light scattering of waxy PSy-ox sample indicated two different color when taken the photo from side and the up in a large jar (Fig. 7, b3 and b4)
PSy85 has been kept at 90◦C for a day for the de-composition of the peroxide groups. After dede-composition,
some new hydroxyl bands at 3.4 and 3.7 can be attributed to new hydroxyl bands appearing in the 1H-NMR
spec-trum. The intrinsic viscosity of the decomposed PSy85 slightly increased after decomposition (ca.η = 0.17 dL/g
Fig. 6. GPC curves of the cold water soluble polymer samples, (a)
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Fig. 7. The picture of the the PSy-ox samples (a) pure soyabean oil, (b) PSy-ox, (c) pure hydroxylated soya oil polymer (NSy-1), (d)
neutral aqueous solution of hydroxylated soya oil polymer (NSy-1); (b1) PSy-ox (oxidation time: 2 months, 10 mm oil layer thickness), (b2) PSy-ox (2 month, 2 mm thickness), (b3-picture from side) PSy-ox (1 mm thickness- 3 months), and (b3-picture in a large jar) PSy-ox (1 mm thickness- 3 months). Thermal decomposition of the oxidized soya oil polymer (PSy85). (Color figure available online.)
for undecomposed PSy85, and 0.20 dL/g for decomposed PSy85).
4 Conclusions
Water soluble hydroxylated soya oil polymers with molec-ular weight 3800–5900 D have been simply synthesized from oxidized soya oil polymer by using diethanol amine. The synthesis conditions obey the main principles of green chemistry. This bio-based water soluble hydroxylated soya oil polymers obtained from the renewable resources can be promising biomaterials for medical and industrial applica-tions. The waterborne polyurethanes based on the hydrox-ylated soya oil polymer should also be important for paint technology.
Acknowledgments
The authors thank B ¨ulent Ecevit University for finan-cial support (Grant# 2011–10—3–02). Helpful discussions with Dr. Kevin Cavicchi are also greatly appreciated.
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