Improvement of 3D Polyester Fabric Surface with Nano Beta-Cyclodextrin and Hydrophilic Silicone and Microemulsion Softeners

Vol-7, Special Issue-Number5-July, 2016, pp1314-1324 http://www.bipublication.com

Research Article

Improvement of 3D Polyester Fabric Surface with Nano Beta-Cyclodextrin and

Hydrophilic Silicone and Microemulsion Softeners

M. M. Jolaei

D Young Researchers and Elite Club,

Science and Research Branch,Islamic Azad University, Faculty of Engineering, Tehran, Iran

ABSTRACT

Modifying of polyester spacer fabric by β-Cyclodextrin may create new characteristics in the product. Using different siloxane including amino ethyl amino propyl polydimethylsiloxane and polyether amino functional siloxane can

produce appropriate softness and lead to relative stability of β-CD on polyester fabric. In this research different

concentration of siloxane compounds as a softener, and β- CD as a modifier are applied and some of the properties of the fabric including weight change, regain, water drop absorption time on fabric surface, chrome ion absorption and reactive dye absorption are studied. Also morphology of fabric surface has been examined by SEM images and chemical structure by FT-IR. We have also studied washing durability of the modified product after 10 times of washing. The results show that increasing of concentration of softener and β-CD leads to obtain a higher gain modification. In comparison of two different based softeners the amino ethyl amino propyl polydimethylsiloxane (AEAP- Silicon) indicates a better durability than the polyether amino functional siloxane (PEA-Silicon).

Key words: Beta cyclodextrin, Nano, Reactive Siloxane, Softener, Spacer Fabric, Polyester,Nanocapsules,

1. INTRODUCTION

Spacer fabric polyester has three dimensional structures, which are obtained from connecting two separate fabrics through connecting threads (threads that create gaps between the two fabrics) with different bending hardnesses [1,2]. Among the characteristics of these fabrics we can refer to air circulation inside the fabric, flexibility, bending, 3D appearance, etc. [2]. Regarding specific technical characteristics, these types of textile are among the technical textiles. Special applications of these fabrics include car seat covers, hospital mats, geotextile, composite, sport, medical cloths, and military industries (Figure1) [3].β-CD are cyclic Oligosaccharides that contain 7 units of D-Glucose with Glucopiranozi and are netted through covalence bonds by C1 and C4 carbons [5,6] and are produced during the

therefore, CD is more stable in pHs more than 3.5 and temperatures above 60 °C

(Figure 2) [4].Β-CDs have a special structure and can be applied in the process of finishing and dyeing [8-11]. They can also be used in controlled release of perfumed materials and guest molecules from cavity as a retarding effect in dyeing and finishing baths and absorbent of smell and as a drug release in the textile industries [5-10,23,24]. Since fabrics are in direct contact with human skin, the toxic specifications of cyclodextrins have been studied [4]. Results indicate that they may be harmful to human bodies in very high concentrations [4]. Since November 13, 2000, β -CD has been introduced as a food additive in Germany. With respect to OECD experiments, this compound of cyclodextrin has no allergic impact [12-14].

Szejtli et al. reported the grafting of CDs onto cellulose fibers by using epichlorohydrin as a cross-linking agent [16]. Buschmann et al. claimed the incorporation of CDs into natural or synthetic materials by a physical means or by chemical paths involving CDs derivatives carrying aliphatic and aromatic groups, chloro carboxylic acids, chloro amino and dimethylol bifunctional compounds as linking agents. Besides, Denter et al. [16] and Reuscher et al. fixed a monochlorotriazinyl β-CD derivative onto different polymer materials including cotton fibers. Finally, they recently proposed a method for grafting CDs onto polypropylene nonwoven fabrics by using the electron beam technology [16]. Furthermore, in another recent study, they have proposed the possibility to fix CDs permanently to cotton and wool fibers by using poly carboxylic acids (PCA) as binding and cross-linking agents [16]. Martel et al. [16] concluded that the mode of grafting occurred through the formation of a cross-linked copolymer between PCA and CDs. This copolymer was not covalently fixed to the fibers, but was physically adhered or was entangled into the fibrous network so that grafting was permanent and resistant to washings [16, 19, 20].

The efficiency of the copolymer created between cross linking agents and CD depends on three factors: curing, the curing time, and the ratio of cross-link agents to CD. According to the pieces of research conducted in this regard, the cross-link agents interact with CD on the fibers in dry environments and thermal fixation temperatures above 140 °C. The curing time has been also considered, at least, 3 minutes for different types of Dextrin [16-20].

Since no evidence of modification of polyester

spacer fabric through β-CD and its stability has been observed, polyester spacer fabric product has been chosen for this research and it has been

modified by β-CD with different softener cross link agents. Besides, we have studied the increased stability of β-CD on spacer fabric polyester product. The feature of this paper could be:

1) Using β-CD on spacer polyester fabric, makes it possible for absorb different materials, 2) The new fabric can be used for absorbing heavy metals such as chromium ion, 3) It becomes possible to dye the product with hydrophilic dyes such as those using for cellulose, 4) It is possible to

increase durability of β-CD on the product by silicon reactive softeners, 5) The specification of the spacer polyester fabric will not change by the modifications used, 6) The fabric finished with environmentally friendly substances, 7) The new fabrics is durable against washing and have special softness.

2. MATERIALAND METHODS

Polyester spacer fabric has been prepared from Bonyad Polypropylene Fiber Production Company (Iran). The over thread is 150 Den, the under thread is 150 Den, the monofilament thread is 30 Den, weight 255 g/m2, and fabric thickness is 3-2 mm. β-CD has been prepared from XI'an Hong Chang Pharmaceutical Co. Ltd. (China). To achieve appropriate acidity, citric acid Merck Co. (Germany) has been used.

100 %

1 1

2 



w

w

w

chemical formula includes amino ethyl amino propyl poly dimethyl siloxane and an almost clear liquid (Figure 3). It has been introduced as a substance with permanent and stable effect against washing and corrosion.

PEA-Silicon softener with trade name of Jet Soft J.1 is a hydrophile softener with excellent softening property which gives a good division to the product and grants a remarkable hydrophilic property to the hydrophobic product. (Figure 4). This softener may be used on different types of fibers and textiles. It is said that this softener (PEA-Silicon) may give a wet-ability property to highly hydrophobic products such as polyester.

First the 20×10 Cm2 samples of desired fabric were prepared and washed. The favorite baths are prepared according to Table 1 for the samples acting with PEA-Silicon softener (J.1) together

with β-CD and according to Table 2 for samples acting with AEAP-Silicon (T.6) together with β -CD.

Then the polyester spacer fabric was put into the favorite bath and after impregnation, passed through pad rolls with 100% pick-up. They are then cured for 3 minutes in the temperature of 100°C and finally the finished product is washed for studying stability. The following bath is used for washing:1g/l nonionic detergent, 1g/l sodium carbonate has been used for 30 min in 70°C.

Experimental section

1) ROTO WASH, made by English Shirley Company, to determine washing stability.

2) UV-2101 from Shiadzu Company, to determine the amount of absorption of Chrome ion.

3) Varian, Cary 500 Model, for the amount of reactive dying in bath.

4) SEM: LEO 440 i made in England, to image of the desired products.

METHODS A) Weight

The weight of the raw material and finished fabric after washing has been measured. This has been done for different samples, and the weight change calculated with formula (1).

Formula (1);

w

w

of finished and washed fabric.

B) Regain

This has been done according to the AATCC Test Method 20A-1981 and calculated by the formula (2).

Formula (2) R%=

W_{= weight of finishing fabric and then}

washed,D= weight of finishing fabric and then dried, R%= Regain%.

C) Water Drop Absorption

At the first, we put the finishing fabric on flat surface then, drop once on the surface by a dropping tube (0.05ml) from 1cm above vertically and then measure the time of drop absorption on the fabric. This is done according to the AATCC Test Method 79-1995.

D) Chrome Ion Absorption

A Solution from potassium dichromate has been prepared and then the samples was put in the solution for 2 hours to adsorb the metal ion. The amount of absorption was obtained from spectrophotometer. The absorption recipe for chrome ion is as follows:

Fabric weight: 11 Cm2samples of 0.3 g, potassium dichromate: 20 mg/g, time=120 min,

temperature: 22-24C,

E) Reactive Dye Absorption

The polyester fabric has been dyed by a reactive dye. The polyester fabric has a compact structure and no side groups to react and provide the

bonding. With finishing by β-CD the reactive groups added to the fabric, for example hydroxyl (OH) groups to dyeing the polyester fabric. The Dyeing recipe is as follows:

Remazol Blue RGB (reactive dye) 4%, spacer polyester fabric 1g, salt 1% weight of fabric (o.w.f), L.R. 40:1(Liquor to Goods Ratio),

water and washing based on general washing prescription are as follows: nonionic detergent

1g/l, sodium carbonate 1g/l, temperature 70C, time 30 min.

F) Durability after 10 Times of Washing

The finished spacer polyester fabric has been washed three times with a cyclic washing machine. Finally subtract the first weight of fabric after finishing obtaining the amount of finishing

materials and β-CD.

The washing prescription are as follows:

This has been done according to the AATCC Test Method (2A)-1996.

RESULTS:

The possible mechanism of reaction of β-CD with softener has been shown in Reaction 1, 2 and 3 and also in Figure (5). This can be done through the chemical and physical reaction that leads to formation of copolymer, this copolymer could be retained in polyester fabric and modified the polyester structure and create special characteristics in the product.

1) R-Si-OH + HO-β-CD R-Si-O-β-CD

2) R-Si-H + H-Si-R R-Si-Si-R + H2

3) R-Si-OH + HO-Si-R R-Si-O-Si-R + H2O

R= AEAP; PEA

According to Figure (5), it is likely that a bond is

created between β-CD and softener in one of the following three ways:

1- Bond between β-CD and softener through hydroxyl and hydrogen reaction groups (Reaction1).

2- Bond between β-CD and softener through final hydrogen (Reaction2).

3- Bond between β-CD and softener through hydroxyl groups (Reaction3).

4- Β-CD could be retained physically in the created network through reactions 2 and 3. As it was shown in Figure 5 the hydroxyl groups of reactive silicon softener can be reacted with hydroxyl groups of beta cyclodextrin. This leads

to crosslinking of beta cyclodextrin on to the polyester fabric and stabilize during washing. The diagram of weight change in Figure (6) shows that the highest percentage is related to sample

number 4 which β-CD and softeners have the most concentration. The order of weight increasing for the samples are as follows:

Sample4 > Sample2 > Sample5 > Sample 3 > Sample 1

Figure (7) indicates the highest regain change percent in the bath number 4, which has the

highest concentration of β-CD and softeners. The regain is more with the increasing of these materials. The order of regain increasing for the samples are as follows:

For PEA-Silicon softener (J.1): Sample4 > Sample2 > Sample5 > Sample3 > Sample 1

For AEAP-Silicon softener (T.6): Sample4 > Sample2 > Sample5 > ample3 > Sample 1

Figure (8) determines the time of drop absorption in seconds, this time delayed with the

increasing of softener and β-CD. For the raw sample this time is zero. The most amount of materials have cause retarding of the time drop in surface of fabric. The coating of this finishing has been caused increasing of drop absorption time. The longest time is in bath number 4 where

softener and β-CD have the most concentration. The order of time drop absorption increase for the samples is as follows:

Sample4 > Sample5> Sample2> Sample1> Sample 3

The mechanism of chrome ion absorption by β -CD on fabric is proposed in Figure (10). As observed in Figure (9) chrome ion absorption changes on different samples after 2 hours in room conditions. The most absorption is in bath number

4 where softener and β-CD have the most

concentration. The cavity of β-CD may cause this characteristic in the treated fabric. The order of chrome ion absorption increase for the samples are as follows:

The schematic of dyeing of the finishing fabric

by β-CD with reactive dye is displayed in Figure (11). Figure (12) shows the reflectance spectrum of samples in 200-800 nm wavelengths and Figure (13) indicates the changes in the amount of reactive dye absorption (K/S). Whatever the

largest amount of β-CD in the fabric finishing might be, the increased hydroxyl groups in fabric finishing and increase in hydroxyl groups caused an increase in the reactive dying in the fabric. These show that the greatest absorption belongs to

the samples containing β-CD and when the amount of hydroxyl (-OH) groups are more in fabrics better dyeing obtains.

For PEA-Silicon softener (J.1): Sample3 > Sample2 > Sample1 > Sample4 > Sample 5

For AEAP-Silicon softener (T.6): Sample5 > Sample3 > Sample1> ample2 > Sample 4

Durability and fixing of finished materials on polyester fabric shows in Figure (14). This indicates that the most finished material on fabric after 10 times of washing in bath number 4, which

β-CD and softener have the largest amount. The order of removed material for the finished samples after 10 times of washing are as follows:

Sample4 > Sample2 > Sample5 > Sample3> Sample1

Figure (15), shows the SEM pictures of raw fabric and finishing fabric. It can be seen that the Fiber surface is flat in raw fabrics but small changes happened when they were treated with softener

and β-CD. Consequently, the finishing materials coated on the fabric surfaces. Also Figure (16) shows a pick in area of 3400 – 3600 cm-1 indicating the hydroxyl groups introduced by

treatment with β-CD on the surface of the finished fabric. This pick is explanatory present of β-CD on fabric surface. There is no such pick in the raw fabric.

4. DISCUSSION

Finishing of spacer polyester fabric is considered for its increased application. This research shows

that using β-CD as an environmental friendly substance, can create new characteristics with

introduction of hydrophile groups and

hydrophobic holes. To increase the durability of β -CD, two types of cross link-agents of PEA-Silicon (J.1) softener and micro emulsion AEAP- Silicon (T.6) have been used, which are capable of reacting with hydroxyl groups of β-CD. The maximum amount of modification are among the complementary samples related to the finished

sample in which concentration of β-CD and softener have their maximum amounts. Also dye-ability of spacer fabric polyester product increases by reactive dyes. Moreover as an absorbent product it has managed to absorb chrome ion. Due to softening characteristics, these substances create appropriate division for the product. From the two substrate in this research, the spacer fabric product finished with β-CD and hydrophile PEA-Silicon (J.1) softener interact better than the sample finished with Micro emulsion silicon softener AEAP-Silicon (T.6).

6. REFERENCES

1. K. Kunde, Spacer Fabrics- their application and future Opportunities, Melliand Textileberichte International Textile Reports, 11-12,(2004)

2. L.Hsieh, Liquid Transport in Fabric Structures. Textile Res. J, 65(5), 299-307(1995).

3. [M.Heide, D.Zschenderlein, U.Mohring, Three-Dimentional Spacer Fabrics in Medicine (IMCEP). 4th International Conference Innovation and Modelling of the Clothing Engineering Processes, (2003). 4. E.M.Martin Del Valle, Review Cyclodextrins

and their uses. Process Biochemistry, 39, 1033–1046, (2004).

5. B.Voncina, V.Vivod, D.Jausovec, Β -Cyclodextrin as retarding reagent in polyacrylonitrile dyeing. Dyes and Pigments, 1-5, (2006).

7. E.Weber, Clathrate Chemistry today – some problems and reflections. Topics in Current Chemistry, 140, 1-20, (1987).

8. P.Savarino, G.Viscardi, P.Quagliotto, E.Montoneri, E.Barni, Reactivity and effects of Cyclodextrins in Textile Dyeing. Dyes and Pigments, 42, 143-147, (1999)..

9. J.Szejtli, Past, present, and future of cyclodextrin research. Pure Appl Chem, 76(10), 1825-1845, (2004).

10. J.Szejtli, Cyclodextrins in the Textile industry. Starch, 55, 191-196, (2003).

11. J.Szetjli, Introduction and General Overview of Cyclodextrin Chemistry. Chem Rev, 1743-53, (1998).

12. RA.Hedges, Industrial applications of Cyclodextrins. Chem Rev, 98, 2035-44, (1998).

13. T.Irie, K.Uekama, Pharmaceutical applications of cyclodextrins. III. Toxicological issues and safety evaluation. J Pharm Sci, 86, 147-62, (1997).

14. T.Loftsson, ME.Brewster, Pharmaceutical applications of Cyclodextrins. J Pharm Sci, 85, 1017-25, (1996).

15. SD.Eastburn, Applications of modified Cyclodextrins. Biotechnol 12,325-39, (1994). 16. B.Martel, M.Morcellet, D.Ruffin, L.Ducoroy, M.Weltrowski, Finishing of Polyester Fabrics with Cyclodextrins and Polycarboxylic Acids as Crosslinking Agents. J of Inclusion Phenomena and Macrocyclic Chemistry, 44, 443-446, (2002).

17. B.Martel, M.Morcellet, D.Ruffin, F.Vinet, M.Weltrowski, Capture and Controlled Release of Fragrances by CD Finished

Textiles. J of Inclusion Phenomena and Macrocyclic Chemistry, 44, 439-442, (2002). 18. 18. Montazer M , Jolaei MM (2010) β -Cyclodextrin stabilized on three-dimensional polyester fabric with different crosslinking agents. Journal of Applied Polymer Science 116 (1):210-217. doi:10.1002

19. 19. Montazer M , Jolaei MM (2010) Novel spacer three-dimensional polyester fabric

with β -cyclodextrin and butane tetra carboxylic acid. Journal of Textile Institute 101 (2):165-172

20. L.Ducoroy, B.Martel, B.Bacquet, M.Morcellet, Ion exchange textile from the finishing of PET fabrics with cyclodextrins and citric acid for the sorption of metallic cations in water. J Incl Phenom Macrocycl Chem, 57,271-277, (2007).

21. L.Ducoroy, B.Martel, B.Bacquet, M.Morcellet, Cation Exchange Finishing of Nonwoven Polyester with Polycarboxylic Acids and Cyclodextrins. J Appl Polym Sci, 103, 3730-3738, (2007).

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Cotton Fiber with Acrylamidomethylated β -Cyclodextrin and its Application. J Appl Polym Sci, 78, 1986-1991, (2000).

23. B.Martel, D.Ruffin, M.Weltrowski, Y.Leckhiri, M.Morcellet, Watere-Soluble Polmers and Gels from the Polycondensation between Cyclodextrins and Poly(carboxylic acid)s: A Study of the Preparation Parameters. J Appl Polym Sci, 97. 433-442, (2005).

24. J.Szetjli, Medical applications of Cyclodextrins. Medicinal Research Reviews, 14(3), 353-86, (1994).

Figure 2. Parts of hydrophobic and hydrophilic of cyclodextrin

Figure 3. Chemical structure of AEAP-Silicon softener (T.6)

Figure 4. Chemical Structure of PEA-Silicon Softener (J.1)

Figure 5.The mechanism of complex formation between silicon softener and β-CD.

2

3 1

0 0.05 0.1 0.15 0.2 0.25 0.3 0.35

%

R

0 1 2 3 4 5

Sa mple s

PEA-(J.1) AEAP-(T.6)

0 1 2 3 4 5 6

%

W

t

1 2 3 4 5

Sa mple s

PEA-(J.1) AEAP-(T.6)

0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2

%

A

b

s

1 2 3 4 5 6

Sam ple s

PEA -(J.1) AEAP-(T.6) 0

100 200 300 400 500 600

T

im

e

(S

e

c

)

1 2 3 4 5

Sa mple s

PEA-(J.1) AEAP-(T.6) Figure(6). The percentages of weight change

Figure(7). The percentages of regain change

Figure(8). Drop absorption on surface of finishing fabric ( seconds)

0 10 20 3 0 4 0 50

200

ط

ا

ﺪھﺎ ﺷ

1ﮫﻧﻮﻤﻧ

2ﮫﻧﻮﻤﻧ

3ﮫﻧﻮﻤﻧ

4ﮫﻧﻮﻤﻧ

5ﮫﻧﻮﻤﻧ

50

40

30

Wave lengt h (nm)

%

R

01

2

3 Sample

200 800

0 0.2 0.4 0.6 0.8 1 1.2

K

/S

0 1 2 3 4 5

Sa mple s

PEA-(J.1) AEAP-(T.6) Figure 10. Mechanism of chrome ion absorption by β-CD on fabric.

Figure 11. Schematic of dyeing of finished fabric by β-CD with reactive dye.

0 0.5 1 1.5 2 2.5 3 3.5 4 4.5

%

W

t

1 2 3 4 5

Sa mple s

PEA-(J.1) AEAP-(T.6)

Figure (13). K/S values of different treated samples

Figure(14).Amount of finished materials after 10 times of washing on the fabric

(b)

(c)

Figure(16). FT-IR spectrums: (a) raw fabric, (b) fabric finished with (J.1),

a

b

c

(c) fabric finished with (T.6)

Table 1- Conditions for preparing baths containing β-CD and PEA-Silicon softener (J.1) Bath number β-CD

(g/l)

Catalyst (CA) (g/l)

Cross-link agents J.1 (g/l)

1 0 10 15

2 50 10 15

3 0 20 30

4 100 20 30

5 100 10 15

Table 2- Conditions for preparing baths containing β-CD and AEAP-Silicon softener (T.6) Bath number β-CD

(g/l)

Catalyst (CA) (g/l)

Cross-link agents T.6 (g/l)

1 0 10 15

2 50 10 15

3 0 20 30

4 100 20 30

5 100 10 15