RJTA Vol. 13 No.

2 2009

Preparation and Characterizations of Fatty Acid / Polyethylene Glycol Condensates and Utilization as Textile Softeners
1

M.H. Abo-Shosha1, F.A. Nassar2, Z. El-Sayed1 and A.G. Hassabo1* Textile Research Division, National Research Centre, Dokki, Cairo, Egypt 2 Faculty of Science, El-Azhar University, Cairo, Egypt

ABSTRACT
Optimal conditions for condensation of equimolar ratios of stearic acid (St) and polyethylene glycol (PEG) 400, i.e. 180C, 8hrs and H2SO4, 4g/kg (reactants mixture), were utilized to condensate the equimolar ratio of stearic (St), palmitic (Pa) or myristic (My) acid with PEG 300, 400, 600, 2000 or 6000. Each of the fifteen condensates was formed by total conversion (83.5 to 84.1 %). Monoesterdiester ratios of the condensates ranged from 4:1 to 49:1. FT IR spectroscopy and hydrophilic lipohilic balances (HLB) of the condensates were also examined. The condensates had softening and hydrophilic properties of cotton fabric with no yellowing at concentrations of 30 and 50g/l in the presence or absence of DMDHEU (50g/l). The presence of DMDHEU improved the fabric resiliency. However, the softening and hydrophilic properties of the fabric were inferior in the presence of DMDHEU rather than the absence. In comparison with a commercial softener, PEG 2000- or 6000-based condensates were higher in fabric wettability and pliability but lower in smoothness. Regarding CRA, only My-2000 was comparable to that of the commercial softener in terms of effect. Keywords: Fatty Acid, Polyethylene Glycol, Condensation, Hydrophilic Lipohilic Balances Softeners

1.

Introduction

presence of a proper acidic catalyst or an Azeotrop in an isotropic distillation. Regarding textile auxiliaries (Slade, 1998), monoesters are used as fibre lubricants, emulsifiers and softeners, whereas diesters are utilized as softeners. Being non-ionic, both are compatible with cationic or anionic textile auxiliaries, and can be used safely in many finishing formulations. Accordingly, the present study is undertaken with a view to a) finding proper conditions for esterification of stearic acid with polyethylene glycol 400 (PEG 400), b) utilizing these conditions in esterification of stearic, palmitic and myristic acids with PEG of different molecular weights, and

The condensation products of fatty acids with polyethylene glycols comprise monoesters and diesters as illustrated in Reactions 1 and 2 (Goldsmith, 1943). RCOOH + HO(C2H4O)nH RCOO(C2H4O)nH + H2O (1) RCOOH + RCOO(C2H4O) nH RCOO(C2H4O)nO CR + H2O (2) Esterification is a state of equilibrium where water must be removed as soon as it is formed. This can be done (Abd Hamid 2004) by carrying out the process at temperatures above 100C and/or in the
* Corresponding author. Tel.: (+49)17664211885; Fax: (+49)2418023301 E-mail address: aga.hassabo@yahoo.com

46

RJTA Vol. 13 No. 2 2009

c) characterizing the condensation products obtained by FTIR spectroscopy and hydrophilic lipohilic balances. Since both monoesters and diesters can be used as textile softeners, the present study extends to evaluation of their capabilities to impart softness to cotton fabric in the presence or absence of the dimethyloldihydroxyethylene urea (DMDHEU) finishing agent. In the second study, these condensates are utilized as emulsifiers in kerosene pigment printing. Textile softeners are widely world because they play an making harsh, pre-treated, fabrics soft and comfortable 2002). used all over the important role in bleached, colored to wear (Achwal,

2.
2.1

Experimental
Materials

2.1.1 Fabrics 100% bleached woven cotton fabric (100 g/m2) was supplied by Misr Spinning and Weaving Co. Mehalla El-Kobra, Egypt. The fabric was prepared by washing at the boiling point for 20 minutes in a solution containing 5g/l Na2CO3 and 2g/l nonionic wetting agent before thorough rinsing and drying at ambient conditions. 2.1.2 Chemicals Polyethylene glycol (PEG) of different molecular weights (300, 400, 600, 2000 and 6000) (Aldrich) as well as three types of fatty acids (Aldrich), myristic (My), palmitic (Pa), and stearic (St), were used. Prior to the reaction, fatty acids and PEGs were dried by heating at 110C for 2hrs in a circulating air oven. Sulfuric acid (98 %), hydrochloric acid (34%) and phosphorus pentaoxide (all from Aldrich) were used as analytical grade catalysts. Dimethyloldihydroxyethylene urea (DMDHEU), a crosslinking agent under the commercial name of ArkofixNG-ET, and HostapalCXET, a nonionic wetting agent, and an alkylaryl polyglycol-based ether, were supplied by Clariant (Egypt). A non-ionic-hydrophilic commercial softener based on a fatty acid ester (the name is not mentioned to avoid any confrontation with the producer was also used for comparing its softening effect with those of the condensates. Magnesium chloride hexahydrate, MgCl2. 6H2O, and glacial acetic acid were used as laboratory grade chemicals. 2.2 Reaction Procedures

Softeners can be classified as cationic, anionic, nonionic and reactive (Hassan, 1998). Nonionic softeners are characterized by excellent compatibility with other ingredients in the finishing bath, effective fibre lubrication and high resistance to discoloration or yellowing (Slade, 1998). However, they are of low affinity for textile and therefore the best method of application is padding. Moreover, they are of limited durability of washing or dry cleaning because they do not form covalent bonds with fibres. Fatty acid/PEG condensates are recommended as fibre lubricants (Slade, 1998) to increase fibretofibre friction (cohesive agents) or decrease fibretofibre friction (softeners) during the mechanical process of synthetic fibres. Depending on both the carbon chain of fatty acid and the repeat units of PEG, a condensate can achieve cohesion or softening (Slade, 1998). Optimum cohesion can be obtained by a fatty acid of C9 or a chain length of C12. Longer carbon chains, such as stearate, generally achieve softening. A chain length of poly (ethylene oxide) of 4 to 6 repeat units has the highest cohesion. Longer chain lengths reduce the extent of fibretofibre friction. For example, PEG (300) pelargonate is an effective cohesive agent and PEG (1000) monostearate is a softening agent (Slade, 1998).
47

The reaction was carried out in a 500ml round flask equipped with the Dean and Stark apparatus. Heating was conducted in a thermostatic oil bath. Except for the case of PEG 6000, 0.1 mole of dried fatty acid and PEG was melted at 60C and thoroughly mixed with a specific amount of catalyst in a 500ml round flask with porcelain balls (2ml in diameter).

RJTA Vol. 13 No. 2 2009

Then, the Danish and Stark apparatus was fitted onto the flask in an oil bath. The temperature rose (85 to 200C) where the reaction happened at different intervals (1 to 12hrs). Then the flask was taken out of the bath, cooled at room temperature, and reaction products were analyzed. The same procedure was applied to the case of PEG 6000, except that the amount of either fatty acid or PEG 6000 was 0.01mole. 2.3 Finishing Method

solution in the funnel was subject to 5 successive washings, each with 75ml of 30 weight percent of the aqueous solution of sodium chloride, to remove the free PEG (Slade, 1998), followed by 5 successive washings, each with 75ml of water to remove salinity and catalyst remnants. Then the ethyl acetate layer was transferred quantitatively to a rotavapour where it was evaporated (in a vacuum at 65 C until drying), leaving the monoester, diester and unreacted fatty acid in a rotvapour flask. The content of the flask was analyzed for both the acid value (ASTM & Method D., 1980-87 &1991) (to determine the content of unreacted fatty acid) and the hydroxyl value (ASTM & Method, E222-88 & 1991) (to determine the terminal hydroxyl content of monoester and also the monoester content). The following calculations are made based on 1 g of the dried content of the flask. Weight of fatty acid =

Fabric samples were treated by padding in a finishing bath containing a condensate (30 or 50g/l), HostapalCXET (2g/l), and acetic acid (2ml/l) in the presence or absence of 50g/l ArkofixNGET and 5g/l MgCl2. 6H2O, to a wet pick up of 80%. Blank sample was padded (100% wet pick up) in a bath having HostapalCXET(2g/l). In the absence of Arkofix NGET, the blank and treated samples were dried (100C /3min); and in its presence they were dried (100C/ 3min), cured (160C/ 4min), and cooled at room temperature for at least 24 hours before testing. 2.4 Analysis and Test Methods

acid value 1 fatty acid molecular weight 1000 56

g/ g sample Weight of monoester =

2.4.1 Percent Total Conversion The extent of conversion of reactants to total esters (mono and di), also known as of total conversion %, was calculated by determining the amount of fatty acid before and after the reaction. This was done by measuring the acid value (ASTM Method D, 1980-87 & 1991) before (A1) and after (A2). Corrections were made to calculate the acid value of catalyst (Ac) as follows. % of Total Conversion =
A1 A2 100 % A1 Ac

hydroxyl value 1 monoester molecular weight 1000 56

g/ g sample Monoester molecular weight = Sum of molecular weights of fatty acid and PEG 18 Weight of diester = 1(weight of fatty acid + weight of monoester) g/ g sample Thus, the ratio of monoester to diester can be calculated. 2.4.3 FT IR Spectroscopy FT IR Spectroscopy was conducted on the ester products of the condensation reaction (the mixture
48

2.4.2 Monoester-Diester Ratio Monoester-diester ratio was determined as follows. An accurately weighted sample (about 5g) of the product (which contains both unreacted reactants and products) was dissolved in ethyl acetate at 35 1C and transferred quantitatively to a 250ml separating funnel to a final volume of 75ml. The

RJTA Vol. 13 No. 2 2009

of monoesters and diesters). The mixture of esters was separated from unreacted fatty acid and PEG by dissolving the products in ethyl acetate at a liquid / product ratio of 10:1 at 35 1C, and transferred to a separating funnel (about 3 times the volume of the ethyl acetate solution). 5 successive washings were given to the ester solution, each with an equivolume amount of the aqueous solution containing NaCl (30 weight percent) and NaOH (2 weight percent to remove the fatty acid and catalyst), followed by 5 successive washings, each of equivolume amount, to remove salinity and remnant alkalinity. The ethyl acetate layer was then evaporated in a rotavapour at 80C in a vacuum until dryness to get the mixture of esters. FT IR spectra were done by the Perkin Elmer spectrum one FTIR with an optical system that conducts data collection over a total range of 7800370 cm-1 with the best resolution of 0.5 cm-1. The samples were prepared for testing by mixing a 1mg sample into 200 mg KBr, forming a disc and scanning in a spectrophotometer. 2.4.4 HLB (Hydrophilic Lipophilic Balance) HLB is evaluated (Slade, 1998; Shenai & Mehra, 1996; Shenai & Saraf, 1995) based on the following equation. HLB = X1 * HLB1 + X2 * HLB2 Where X1 and X2 are the weight fractions of monoester and diester in their mixture respectively, and HLB1 and HLB2 are HLB for monoester and diester respectively. Each of HLB1 and HLB2 is calculated according to the formula (Slade, 1998; Shenai, 1995). HLB =

Table 1. Connection between the HLB-Number and the Function Expected from the Surfactant in Aqueous Solution (Tomasino 1992) HLB Surfactant application Number Antifoaming agents 1-3 3-6 7-9 8-18 12-16 15-18 2.4.5 Fabric Testing The dry crease recovery angle (CRA) is measured by AATCC Test Method 66 1990. Fabric roughness was measured by Surface Roughness Measuring Instrument SE 1700 a. Fabric stiffness was determined according to ASTM Test Method D 1388 96 E1 using the cantilever apparatus. Wettability was evaluated by AATCC Test Method 39 1993. Yellowing index was evaluated by the Color-Eye 3100 specrophotometer supplied by SDL inter, England (Welch & Peter, 1997). W/O emulsifiers Wetting agents O/W emulsifiers Detergents Solubilisers

3
3.1

Results and Discussion

Preparation

3.1.1 Selection of Catalyst Stearic acid (StCOOH) reacted with an equimolar ratio of PEG 400 in the absence or presence of several acid catalysts (eg. HCl, H2SO4 and P2O5) at 150C for 4 hours. Esterification usually brings about a mixture of monoesters and diesters as follows: 3 St COOH + 2 HO(CH2CH2O)xH

100 (formula weight of hydrophilic part) 5 (formula weight of the compound)

A more detailed connection between the value of the HLB number and the function of the surfactant is shown in Table 1.

StCOO(CH2CH2O)xH + StCOO (CH2CH2O)x OCSt+3 H2O (4) The dependence of total conversion % on the type of catalyst is shown in Table 2.

49

RJTA Vol. 13 No. 2 2009

Table 2. Effect of Catalyst Type on Total Conversion % of St400* Condensate

Catalyst Type None HCl H2SO4 P2O5 Total Conversion % 20.2 40.2 60.4 22.7

(b) a higher removal of water of reaction, i.e. favouring an ester formation. However, an adequate supply of reactants with enough energy at higher temperatures to overcome the activation energy barrier of reactions cannot be ruled out (Ibrahim et al., 2003). Raising the temperature from 130 to 200C was accompanied by little enhancement in total conversion %, suggesting that 180C can be an optimal choice of esterification temperature in the employed conditions. Table 3. Effect of Temperature on Total Conversion % of St- 400* Condensate Total Conversion %

Molar ratio of stearic acid to PEG 400: 1:1; temperature: 150C; time: 4 hrs: catalyst: 3 g (/kg reactants mixture) Stearic acid PEG 400

It was noted that (a) the total conversion % was higher in the presence than the absence of catalysts manifesting the role of catalysts in higher conversion (Chen, Xu & Okuhara,1999), and (b) the effectiveness of catalysts to achieve esterification shows the descending order of activity as follows: H2SO4 > HCl > P2O5 > none. The order was the same as that of acidic strength, which accentuated the role of acidity in the overall activity. Although P2O5 is a dehydrating agent removing the water of reaction (producing ortho phosphoric acid) and shifting the equilibrium of Reaction 4 to the right, it had the lowest activity among the acids used. This can be attributed to the lowest acid strength of ortho phosphoric acid, which again manifests the role of acid strength in the overall activity. 3.1.2 Temperature Esterification was carried out using stearic acid with a PEG 400 molar ratio of 1:1 in the presence of sulfuric acid at different temperatures (85 200C) for 4 hours. The results are shown in Table 3. It is obvious that raising the temperature from 85 to 130C is accompanied by a significant enhancement in total conversion %. This can be associated with (a) the increase in fluidity and mobility of reactants heightening the probability of their fruitful collisions and
50

Temperature (C)

85 39.2 100 48.1 130 56.3 150 60.4 180 63.5 200 65.1 Molar ratio of stearic acid to PEG 400:1:1; time: 4hrs; [H2SO4]: 3g (/kg reactants mixture). * Stearic acid PEG 400 3.1.3 Sulfuric Acid Concentration In this phase of the study, the equimolar mixture of stearic acid and PEG 400 reacted at 180C for 4 hours using different concentrations of sulfuric acid catalyst (0 5g / kg reactants mixture). The results are shown in Table 4. Table 4. Effect of Sulphuric Acid Concentration on Total Conversion % of St400* Condensate H2SO4, g/kg Total Conversion %

0 27.2 1 40 2 52.2 3 63.5 4 71.7 5 72.1 Molar ratio of stearic acid to PEG 400: 1:1; temperature: 180C; time: 4hrs * Stearic acid PEG 400

RJTA Vol. 13 No. 2 2009

The total conversion % in the absence of the catalyst was 27.2 %. The reaction in the presence of 1g acid (/kg reactants mixtures) resulted in the total conversion % of about 1.5 times more than in the absence of the catalyst. The result signifies the role of sulfuric acid in enhancing the capability of reactants to undergo esterification. Increasing the concentration in the range of 0.5 to 4g (/kg reactants mixture) was accompanied by a remarkable increase in total conversion %. At a concentration of 4g (/kg reactants mixture), the total conversions % was about 2.5 times more than in the absence of the catalyst. Increasing the concentration beyond 4g (/kg reactants mixture) and up to 5g (/kg reactants mixture) was accompanied by a negligible increase in total conversion %. 3.1.4 Time Table 5 shows the effect of time on total conversion % of esterification of stearic acid with PEG 400 at a molar ratio of 1:1 at 180C using 4g sulfuric acid /(kg reactants mixture). Table 5. Effect of Time on Total Conversion % of St- 400* Condensate Time (h) Total Conversion % 39.2 47.1 58.3 71.7 77.3 83.5 84.8 85.2 to PEG 400: 1:1; 4g (/kg reactants

3.1.5 Fatty Acids and PEG Molecular Weight Stearic, palmitic and myristic acids were each esterified with PEG of molecular weights ranging from 300 to 6000 at 180C for 8 hours in the presence of 4 g/kg sulfuric acid as the catalyst. The total conversion %, the monoester-diester ratio and the hydrophilic lipohilic balances of the condensate are shown in Table 6. It is evident that the total conversion in all cases was reasonably high, having values of 83 to 84 % under the employed experimental conditions, regardless of the used fatty acid or PEG. Table 6 also reveals that a) the monoester / diester ratio increased after the PEG molecular weight increased for the same acid, and the ratio of monoester to diester decreased after the fatty acid molecular weight decreased for the same PEG.

b)

1 2 3 4 6 8 10 12 Molar ratio of stearic acid temperature: 180C; H2SO4: mixture). * Stearic acid PEG 400

These phenomena can be associated with the concentrations of active sites on acids and PEG (i.e. carboxyl and hydroxyl groups). That is, after the PEG molecular weight increased for the same acid, the concentrations of both of the carboxyl and hydroxyl groups decreased. This led to lower concentrations of both of them for diesterification (Reaction 2) after performing mono esterification (Reaction 1). The opposite held true in the case of decreasing the fatty acid molecular weight for the same PEG, when the concentrations of both the carboxyl and hydroxyl groups increased. In this case, a relatively higher amount of each group was available for diesterification after performing mono esterification. Concerning hydrophilic lipohilic balances, the following points are summed up comparing the values in Table 6 with those of surfactants in aqueous solutions (Slade, 1998; Shenai, 1995) (see Table 1): a) All condensates, except the PEG 6000-based ones, had HLB's ranging from 9.55 to 17.87, and these values were within the range of

The reaction happened at a high rate initially, slowed down over time and then levelled off (in the range of 8 to 12 hours), due to reactant consumption, and concentration reduction, by time. It is also clear that the reaction reached a high level at the final stage of conversion. For example, a total conversion of 83.5 % was observed after 8 hours.

51

RJTA Vol. 13 No. 2 2009

oil-in-water (o/w) emulsifiers (i.e. the range of 8 18). b) HLB's of St600, Pa600 and My600 were 13.34, 13.70 and 14.12 respectively, which fell in the range recommended for detergents (i.e. the range of 12 16). HLB's of St2000, Pa2000 and My2000 were 17.45, 17.65 and 17.87 respectively, d)

which fell in the range recommended for solubilisiers (i.e. the range of 1518). HLB's of St6000, Pa6000 and My6000 were 19, which is very close to the value of PEG (i.e. 20). Accordingly, it is expected that their behaviours in aqueous solutions are more similar to PEG 6000 than the parent fatty acids.

c)

Table 6. Total Conversion %, Monoester-Diester Ratio and HLB of Condensate Formed by Different Fatty Acids and PEGs
Fatty Acid Type PEG, mol. wt 300 400 Stearic 600 2000 6000 300 400 Palmitic 600 2000 6000 300 400 Myristic 600 2000 Total Conversion % 83.5 83.8 83.7 83.9 83.8 83.6 83.5 83.7 836 83.9 83.7 84.0 84.1 83.8 Monoester-diester ratio 07: 1 18: 1 27: 1 31: 1 49: 1 06: 1 12: 1 15: 1 24: 1 34: 1 04: 1 10: 1 11: 1 22: 1 HLB Designation of condensate St300 St400 St600 St2000 St6000 Pa300 Pa400 Pa600 Pa2000 Pa6000 My300 My400 My600 My2000

9.55 11.31 13.34 17.45 19.08 10.0 11.73 13.7 17.65 19.16 10.36 12.23 14.12 17.87

My6000 19.25 32: 1 83.9 6000 Molar ratio of fatty acid to PEG: 1:1; temperature: 180C; time: 8hrs; H2SO4: 4 g (/kg reactants mixture).

3.1.6 FT IR Spectroscopy The spectra of the fifteen purified condensates in comparison with the parent acids and PEGs were obtained as described above. The general view of these spectra was similar with variations concerning the intensity of bands. Three of the spectra are reported here for the sake of illustration. They are St-400, Pa-600 and My-2000
52

as shown in Figures 1, 2 and 3. In each illustration, the FT IR spectra of a condensate (Curve C), its parent PEG (Curve A) and the fatty acid (Curve B) are shown. The spectra showed a band at 1105 cm-1 in Curve A and Curve C, representing the COC bond. Also, in the case of fatty acids (Curve B), the band of OH stretching vibration appeared at 2848

RJTA Vol. 13 No. 2 2009

2917 cm-1, and the CH stretching band at 2953 2955 cm-1 was superimposed on the OH stretching band (Silverstein, 1991). However, in the case of PEGs, the band of OH stretching vibration was found at 33893420 cm-1 (Silverstein, 1991) and the CH stretching band at 2870 2890 cm-1 was separated from the OH stretching band . The spectra showing the ester band (Curve C) at 1734 1737 cm-1 (Silverstein, 1991) can be attributed to the formation of a carbonyl bond, resulting in the reaction between hydroxyl and carboxyl groups. This band was not observed in the spectra of PEGs (Curve A) but noticed in the spectra of fatty acids (Curve B) at a low value of 1698 1701 cm-1 (carbonyl group band for

carboxylic acid). Also, the intensity of the band of OH stretching vibration at 3389 3420 cm-1 in Curve (C) was weaker than that in Curve (A) (Abo-Shosha et al, 2005) , and the CH stretching band was separated in the product. It can be concluded (Dean1995; Pravia et al. 2001) that the intensity of the band of OH stretching vibration was lower in Curve (C) than Curve (A) because of its consumption in esterification. The ester group appeared in the IR spectra of the condensates.

120

A
100

T (%)

80

60

40 4000 3500 3000 2500 2000

-1

1500

1000

500

Wave number (cm )

100

80

T (%)

60

40

20

0 4000

3500

3000

2500

2000
-1

1500

1000

500

Wave number (cm )

53

RJTA Vol. 13 No. 2 2009

120

100

80

T (%)

60

40

20

C
3500 3000 2500 2000
-1

0 4000

1500

1000

500

Wave number (cm )

Fig. 1. FT-IR of Reactant and Product of Reaction between PEG 400 & Stearic Acid- A: PEG 400, B: Stearic Acid and C: Product St400
120

100

T (%)

80

60

A
40 4000 3500 3000 2500 2000
-1

1500

1000

500

Wave number (cm )

100

B
80

T (%)

60

40

20 4000

3500

3000

2500

2000
-1

1500

1000

500

Wave number (cm )

54

RJTA Vol. 13 No. 2 2009

120

100

80

T (%)

60

40

20

C
3500 3000 2500 2000
-1

0 4000

1500

1000

500

Wave number (cm )

Fig. 2. FT-IR of Reactant and Product of Reaction between PEG 600 & Palmitic Acid- A: PEG 600, B: Palmitic Acid and C: Product Pa600

120

100

T (%)

80

60

A
40 4000 3500 3000 2500 2000
-1

1500

1000

500

Wave number (cm )

120

100

T (%)

80

60

40 4000

3500

3000

2500

2000
-1

1500

1000

500

Wave number (cm )

55

RJTA Vol. 13 No. 2 2009

110 100 90 80 70 60 50 40 4000

T (%)

C
3500 3000 2500 2000
-1

1500

1000

500

Wave number (cm )

Fig. 3. FT-IR of Reactant and Product of Reaction between PEG 6000 & Myristic Acid- A: PEG 6000, B: Myristic Acid and C: Product My6000 3.3 Utilization of the Condensate as Textile Softeners condensates or the commercial softener in the absence of DMDHEU. Regardless of the softener concentration and type, the treated fabric had a noticeable enhancement in both smoothness and pliability as a result of reduced stiffness and roughness in comparison with the blank sample. The higher the softeners concentration was, the greater the improvement in the softening effect became, It is also obvious that hydrophilicity, also known as wettability, was impaired after treatment by either the condensates or the commercial softener, and this defect was more noticeable at a concentration of 50 g/l than at 30g/l. The increase in the molecular weight of PEG in a condensate of fatty acid coincided with a drop in stiffness and wettability and an increase in roughness. This can be attributed to the increase in hydrophilicity and absorption of the condensate by the fabric components (yarns and fibres) at the expense of decreased deposition on the fabric surface which gives rise to reduced wettability, lower stiffness and higher roughness. The same observation holds true for the case of decreasing the fatty acid chain length for the same PEG molecular weight, for example, going from St600 through Pa600 or My600. This can be ascribed to.the decrease in hydrophilicity and the increased deposition of the condensate on the fabric surface on the expense of penetrating inside its structure.

The unique structures of the prepared condensates allow them to give textiles a softening effect. They have polyether and fatty chain moieties of different lengths. The first has fabric hydrophilicity, a property missing in most commercial softeners. The second supplies the fabric with smoothness and pliability. The relative lengths of the two moieties determine if the condensate prefers to reside on the surface (enhanced smoothness) or penetrate the the fabric structure (improved pliability or reduced stiffness). Accordingly, the softening effect in this study is evaluated by measuring surface roughness and fabric stiffness. The following are the results of utilizing these condensates as softeners for cotton fabric in the presence of absence of DMDHEU in comparison with the commercial softener. 3.3.1 The Condensates as Softeners in the Absence of DMDHEU Tables 7 shows the stiffness, roughness, wettability and yellowing index (YI) of a cotton fabric treated with 30 and 50 g/l of different
56

RJTA Vol. 13 No. 2 2009

Table 7. Stiffness, Roughness, Wettability and Yellowing Index (YI) of Cotton Fabric Treated by Different FA/PEG Condensates in Absence of DMDHEU Types of Softener Conc. (g/l) Softener 30 g/l 50 g/l Stiffnes Roughne Wettabilit YI Roughne Wettabi YI Stiffness s ss y ss lity mg. cm mg. cm m Sec. m Sec. Blank* 25004 19.90 3 3.59 25004 19.90 3 3.59 Commercial 14887 14.41 90 3.75 13265 13.63 120 3.74 St300 18224 13.22 150 3.80 17521 12.12 180 3.72 St400 17345 14.54 120 3.85 16313 12.45 140 3.74 St600 16923 15.12 100 3.70 16022 13.22 125 3.78 St2000 16124 16.17 70 3.77 15125 14.11 90 3.67 St6000 16001 17.22 30 3.79 14331 15.01 40 3.85 Pa300 17812 13.88 144 3.81 17112 12.71 171 3.76 Pa400 16413 14.92 113 3.68 16012 13.52 122 3.75 Pa600 15121 15.23 95 3.74 14821 14.62 110 3.69 Pa2000 14782 16.53 53 3.66 14126 14.96 74 3.73 Pa6000 14124 17.82 21 3.71 13411 15.32 29 3.76 My300 17125 14.22 140 3.8 16522 13.22 161 3.69 My400 16021 15.31 100 3.78 15124 13.88 107 3.76 My600 14723 15.67 82 3.67 14237 15.21 90 3.77 My2000 14112 16.92 42 3.60 13421 15.92 55 3.73 My6000 13811 18.21 20 3.65 13128 17.01 24 3.77 (*) HostapalCXET: 2 g/l; wet pick up: 100 %; drying at 100C/3min Comparing the softening efficiency of the condensates with that of the commercial softener reveals that the combined effect of the latter cannot be achieved by any of the condensates. Some of the condensates are inferior to the commercial softener in terms of stiffness. However, they perform better when it comes to some properties, such as roughness and wettability. When it is hot and humid, the wettability of a finished fabric is a decisive factor in comfort (Abd-el Halim, 2003). It seems that Pa2000, Pa6000, My 2000 and My6000 are superior to the commercial softener in terms of wettability, and they bear comparable values of stiffness and roughness at concentrations of 30 and 50g/l. The yellowing of fabrics, also known as YI, was comparable to that of the commercial softener after treatment by the condensates. The YI of softened fabrics was slightly higher than that of blank fabrics (increasing from 3.59 to an average of about 3.75).
57

3.3.2 The Condensates as Softeners in Presence of DMDHEU The values of stiffness, roughness, wettability, dry crease recovery angle (CRA) and YI of the cotton fabric treated with 30 and 50g of different condensates or the commercial softener in the presence of 50 g/l DMDHEU are shown in Table 8. It is clear that the treatment of the cotton fabric by DMDHEU, in the absence of a softener, increased its stiffness, roughness and time for water absorption. However, it improved fabric resiliency, also known as CRA. This is the direct consequence of crosslinking cellulose chains with DMDHEU (Tomasino, 1992; Abo-Shosha et al., 2007). The inclusion of the commercial softener in the finishing bath, regardless of the concentration, improved pliability, smoothness and resiliency of the fabric. This can be associated (Gaffar, 2000) with a) a coating and/or encapsulating of cellulosic

RJTA Vol. 13 No. 2 2009

fibres with a softener enhancing smoothening, b)

film,

thereby

c)

improving the characteristics.

fabrics

smooth

drying

reducing inter yarn and inter fibres friction, and

The impairment of fabric wettability can be ascribed to the fatty acid moiety of the commercial softener.

Table 8. Stiffness, Roughness, Wettability, Resiliency and Yellowing index (YI) of Cotton Fabric Treated with Different Condensates in Presence of DMDHEU
Types of Softener Softener Conc. (g/l) Roughness m 19.9 20.3 16.84 14.61 15.21 16.17 17.13 17.75 15.21 15.82 16.89 17.61 18.22 16.51 17.11 17.93 18.31 18.61 30 g/l Wettability Sec. 3 6 100 161 140 122 90 45 152 131 110 80 32 145 120 103 70 25 CRA (W+F) 181 260 278 227 241 241 246 237 254 260 263 267 246 259 263 270 271 266 YI 3.59 3.83 3.89 3.92 3.81 3.80 3.85 3.89 3.81 3.83 3.79 3.71 3.89 3.87 3.78 3.75 3.77 3.86 Stiffness mg. cm 25004 26127 19741 23234 22151 21826 20516 20115 22511 21618 20711 19821 19125 21621 20611 19822 19311 18351 50 g/l Roughness Wettability m Sec. 19.9 3 20.3 6 16.32 125 15.22 188 15.61 149 16.82 131 17.69 95 18.11 50 15.93 175 16.81 139 17.65 121 18.11 90 19.10 43 17.11 153 17.51 131 18.11 92 18.52 61 18.81 32 CRA (W+F) 181 260 285 235 250 255 260 255 260 265 270 263 260 263 267 269 274 267 YI 3.59 3.83 3.88 3.85 3.86 3.88 3.80 3.91 3.82 3.84 3.80 3.84 3.85 3.81 3.87 3.86 3.88 3.89

Stiffness mg. cm Blank* 25004 None 26127 Commercial 20132 St300 24000 St400 23121 St600 22911 St2000 21945 St6000 21321 Pa300 23612 Pa400 22734 Pa600 21952 Pa2000 21146 Pa6000 20915 My300 22134 My400 21831 My600 20923 My2000 20121 My6000 19925

(*) HostapalCXET: 2 g/l; wet pick up: 100 %; drying at 100C/3min DMDHEU: 50 g/l; HostapalCXET: 2 g/l; MgCl2.6H2O: 5 g/l; acetic acid: 2 ml/l; wet pick up: 100 %; drying at 100C/3min.; curing at 160C/3 min The inclusion of condensates in the finishing bath has in general a favourable effect on fabric smoothness. This effect depends on the structure of the condensate. It was found that the increase in the chain length of PEG for the same fatty acid coincided with the decrease in both the stiffness and wettability time and the increase in the roughness. This can be attributed to the hydrophilicity and lubricant effect. Another finding was that the resiliency of fabric was lower in the presence of the condensates. This could be associated with the consumption of the methylol groups of DMDHEU reacting with the terminal OH groups of monoester in the condensate, rather than crosslinking cellulose
58

chains (Abo-Shosha and Ibrahim, 1992). The blocking factor cannot be ruled out when the resiliency decreased from myristic acid, stearic acid to palmitic acid at the same PEG molecular weight. This can be associated with the increase in hydrophobicity and the molecular structure from myristic acid to stearic acid. The extent of surface deposition of the condensate also increased in the same direction. This resulted in blocking the fabric structure towards the DMDHEU diffusion. The same effect could be observed after increasing the PEG molecular weight from 300 to 2000, regardless of the fatty acid, where the resiliency increased and then

RJTA Vol. 13 No. 2 2009

decreased after the PEG molecular increased to 6000. The same rule also goes for the softening efficiency of condensates in comparison with the commercial softener. It is obvious that yellowing (YI), though unnoticed by human eye, is mainly caused by thermal treatment as YI in absence of softeners is comparable to YI in their presence regardless of softeners. However, it is important to state that PEG 2000or 6000-based condensates are superior in terms of fabric wettability and pliability but have lower smoothness when compared with the commercial softener. Regarding CRA, only My-2000 is comparable to the commercial softener (an insignificant difference of about 7-11). Moreover, no visual yellowing is detected by human eyes when treating the fabric by the condensates or commercial softener.

softening effect, in terms of stiffness and surface roughness, and the hydrophilic effect, also known as wettability, depend on the fatty acid and PEG molecular weights. When the PEG molecular weight was constant, increasing the fatty acid chain length resulted in the increase in stiffness and wetting time and also the decrease in surface roughness. On the other hand, increasing the PEG molecular weight resulted in the decrease in stiffness and wetting time. While increasing the surface roughness of the treated fabric, the pliability and smoothness obtained by the commercial softener could not be compared by the condensates because some of the condensates were inferior to the commercial softener in terms of stiffness. The softening and hydrophilic effects were more noticeable at a concentration of 50 g/l than at 30 g/l. The inclusion of DMDHEU in the finishing formulation containing a condensate improves the CRA. The values of fabric stiffness, roughness and wettability are higher in the presence of DMDHEU, regardless of the type of softener. The PEG 2000- or 6000-based condensates have superior fabric wettability, pliability and lower smoothness when compared with the commercial softener, and produce comparable CRA results. No visual yellowing was noticed by human eyes when treating the fabric by the condensates or commercial softener.

4.

Conclusions

Fifteen fatty acid/PEG condensates, based on St, Pa and My acids along with PEG 300, 400, 600, 2000 and 6000, were prepared when the acid reacted with PEG at an equimolar ratio at 180C for 8 hours using 4g/l H2SO4. The total conversion % was high (85.5 to 84.1%). The monoester/diester ratio of the condensates ranged from 4:1 to 49:1, and increased by increasing (decreasing) molecular weight of PEG (acid). HLB reveals that a) all condensates, except the PEG 6000-based ones, can be used as o/w emulsifiers, My300 can be used as a wetting agent, St600, Pa600 and My600 can be used as detergents, and St2000, Pa2000 and My2000 can be used as solubilisers.

REFERENCES
[1] Abd Hamid, S.B., Abdullah, F.Z., Ariyanchira, S., Mifsud, M., Iborra, S. & Corma, A. 2004, Polyoxyethylene Esters of Fatty Acids: An Alternative Route for High Selectivity of Monoesters, Catalysis Today, vol. 97, no. 4, pp. 271 - 276. AbdEl-Halim, N.A. 2003, Thesis Effect of Some Constructions, Pretreatment and Finishing of Woven Cellulosic Fabrics on Some Functional and Care Properties, Ph.D Thesis, Menoufia University, Cairo, Egypt. AboShosha, M.H. & Ibrahim, N.A. 1992, Water Soluble Polyether Polyurethanes as Finishing Additives in Easy Care Finishing of Cotton Fabrics, Science International

b) c)

[2]

d)

The FT IR spectra of condensates indicate the presence of ester groups. The unique structures of the condensates suggest that they can be used as hydrophilic softeners for cotton fabric. Both the
59

[3]

RJTA Vol. 13 No. 2 2009

(Lahore), vol. 4, no. 2, pp. 163. Abo-Shosha, M.H., El-Hosamy, M.B., Hashem & El-Nagar, A.H. 2007, A leaching type antibacterial agent I the easy care finishing of knitted cotton fabric, J. Industrial Text, vol. 37, no. 1, pp. 55-77. [5] Abo-Shosha, M.H., El-Sayed, Z.M., Fahmy. H.M. & Ibrahim, N.A. 2005, Synthesis of PEG/TDI/F6 Adducts and Utilization as Water/Oil Repellents and Oily Stain Release Finishes for Cotton Fabric, Polymer Plastics Technology and Engineering, vol. 44, pp. 1189- 1201. [6] Achwal, W.B. 2002, Textile Softeners and their Application Possibilities, Colourage, vol. XLIX, no. 9, pp. 69 - 70. [7] Chen, X., Xu, Z. & Okuhara, T. 1999, Liquid Phase Esterification of Acrylic Acid with 1-Butanol Catalyzed by Solid Acid Catalysts, Appl. Catal. A: General, vol. 180, no. 3, pp. 261 - 269. [8] Dean, J.A. 1995, Analytical Chemistry Handbook, McGraw-Hill, New York. [9] Gaffar, M.A. 2000, Chemical Modification of Cellulose Fibers Using Carboxylic Acids, PhD Thesis, Ain Shams University, Cairo. Egypt. [10] Goldsmith H.A. 1943 "Polyhydric Alcohol Esters of Fatty acids", Chem. Rev. 33 (3), 257 - 349. [11] Hassan, T.M. 1998, Effect of Bio Finishing on Dyeing Properties of Cellulosic Fabrics, PhD thesis, Helwan University, Cairo,
[4]

Egypt. [12] Ibrahim, N., Rashed, M.M. & Abo-Shosha, M.H. 2003, Polyacrylamide Guar Gum adduct as a New Thickener for Reactive Printing of Wool and Nylon 6, Polymer Plastics Technology and Engineering, vol. 42, no. 5, pp. 757-777. [13] Pravia, D.L., Lampman, G.M. & Kritz, G.S. 2001, Introduction to Spectroscopy, 3rd ed., Harcourt College Publisher, San Diego, New York. [14] Shenai, V.A. & Mehra, R.H. 1996, Technology of Textile Processing, Evaluation of Textile Chemicals, Second Edition, Sevak Publications, Mumbai, vol. 8, pp. 88. [15] Shenai, T.M. & Saraf, N.M. 1995, Technology of Textile Processing, Chemistry of organic textile chemicals, Second Edition, Sevak Publications, Mumbai, Chap XI vol. 5 & 7, pp. 311. [16] Silverstein, R.M., Basster, G.C. & Morrill, T.C. 1991, Spectrometric Identification of Organic Compounds, Fifth Edition, John Wily & Sons, Inc., New York, Chap. 3, pp. 91. [17] Slade, P.E. 1998, Handbook of Fibre Finish Technology, Marcel Dekker, Inc. New York. Chap. 5, pp. 129, and Chap. 6, pp. 185. [18] Welch, C.M. & Peter, J.G. 1997, Mixed Polycarboxylic acid & mixed catalyst in formaldehyde free durable press finishing, Text. Chem. Color., vol. 29, no. 22.

60