Preparation of novel chitosan derivatives and applications in functional finishing of textiles

Journal Pre-proofs Preparation of novel chitosan derivatives and applications in functional finishing of textiles Hong Pan, Tao Zhao, Lihui Xu, Yong Shen, Liming Wang, Ying Ding PII: DOI: Reference:

S0141-8130(19)33599-8 https://doi.org/10.1016/j.ijbiomac.2019.10.226 BIOMAC 13727

To appear in:

International Journal of Biological Macromolecules

Received Date: Revised Date: Accepted Date:

16 May 2019 17 October 2019 24 October 2019

Please cite this article as: H. Pan, T. Zhao, L. Xu, Y. Shen, L. Wang, Y. Ding, Preparation of novel chitosan derivatives and applications in functional finishing of textiles, International Journal of Biological Macromolecules (2019), doi: https://doi.org/10.1016/j.ijbiomac.2019.10.226

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Preparation of novel chitosan derivatives and applications in functional finishing of textiles Hong Pana,*, Tao Zhaob, Lihui Xua, Yong Shena, Liming Wanga, Ying Dinga, aCollege

of Fashion and Textiles, Shanghai University of Engineering Science, Shanghai, China

bCollege

of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai, China

ABSTRACT: A novel chitosan derivative, O-acrylamidomethyl-N-[(2-hydroxy-3dimethyldodecylammonium) propyl] chitosan chloride (NMA-HDCC), was synthesized by reacting chitosan (CTS) with epoxypropyl dodecyl dimethyl quaternary ammonium salt and N-methylolacryl amide (NMA). The chemical structure of the quaternized chitosan was analyzed by FTIR and NMR. The water soluble derivative can form covalent bonding with cellulosic fibers and bring quaternary

salt groups onto the fibers. Anti-

bacterial as well as salt-free reactive dyeing properties of the treated cotton samples were analyzed. The NMA-HDCC treated cotton fabrics showed durable antimicrobial functions even after 30 consecutive home launderings. The cotton treated with the chitosan and different chitosan derivatives showed improved uptakes, fixation rates, K/S values and fastness of reactive dyes without using auxiliary salt. Key words: anti-bacterial; salt-free dyeing; chitosan, quaternary ammonium salt 1. Introduction Chitosan, a natural polymer, possesses several outstanding properties such as antimicrobial activity, non-toxicity, bio-degradability and bio-compatibility

[1-3].

The

excellent antimicrobial property of chitosan makes it possible to produce eco-friendly antimicrobial textile goods. Due to the cationic nature, chitosan can substitute certain toxic chemicals in providing functional performance, as well as assistance to salt-free reactive dyeing of cotton fabrics [4]. Most important, the chitosan-based textile additives is bio-degrability, thus could decrease the environmental protection pressure. Based on these unique properties, chitosan is considered as an excellent candidate as textile

1

additives and finishing agent. Applications of chitosan and its derivatives in textile dyeing and finishing have been reported in recent years

[5-6].

However, due to the cationized

amine nature, chitosan derivatives could lose the functional activity under alkaline conditions [7-8], and also the chitosan structures may have poor durability on surfaces of textiles without chemical bonding with fibers

[9],

which greatly limits the application

potential of chitosan. Quaternization of the amine groups is an efficient solution for chitosan to provide stable cationic structure over a broad pH range [10-12] and improve antimicrobial functions of the materials treated by the derivatives. Quaternized chitosan derivatives with simple structure have received considerable attention in many fields

[13-15].

Comparing with

simple alkyl group [4], long chain hydrophobic alkyl group possesses lower surface energy and stronger adsorption function on bacteria, which can enhance membrane permeability and accelerate cell dissolution [16]. The antibacterial property of antimicrobial agent can be improved by introducing proper long chain alkyl group. Besides, the finish agent with long chain alkyl can give soft hand feel to the fabric

[17].

The introduction of dodecyl

quaternary ammonium salts and reactive groups onto chitosan backbone are expected to improve the antibacterial properties and form covalent bonds with fibers. To date, there are few studies focused on the chitosan derivative with long chain alkyl quaternary ammonium salt and reactive groups that can react with fiber groups. According to this approach, an epoxypropyl dodecyl dimethyl quaternary ammonium salt was designed and synthesized, and then connected to chitosan and converted to a fiber reactive derivative. The chitosan derivative of this quaternary ammonium salt, O-acrylamidomethyl-N-[(2-hydroxy-3-dimethyl dodecylammonium) propyl] chitosan chloride (NMA-HDCC) was thus prepared. This compound is easily soluble in water in a broad pH range [18], and also possesses good antimicrobial function and can form covalent bond with hydroxyl group in cellulose. The anti-bacterial as well as the salt-free reactive dyeing properties of the modified products were analyzed in detail. 2. Experimental 2.1 Materials 2

Industrial grade dyes, C.I. Reactive Red 2, C.I. Reactive Black 5 (structures are shown in Figure 1) were used. N,N-Dimethyldodecylamine was purchased from Acros Organics with a purity of 87%. Chitosan (85% of deacetylation with the average molecular weight at 3.0*105) and other chemicals were supplied by Sinopharm Chemical Reagent Co. Ltd and were used without further purification.

Figure 1 Structures of C.I. Reactive Red 2 (a),C.I. Reactive Black 5 (b)

Nutrient agar and nutrient broth were purchased from Sinopharm Chemical Reagent Co. Ltd. Escherichia coli (Gram-negative, CMCC44113) was obtained from biological laboratory of Donghua University in China. Bleached and desized cotton cloth was used in anti-bacterial and salt-free reactive dyeing experiment. 2.2 Synthesis and characterization of chitosan derivatives

n=11 Scheme 1 Synthetic procedures of NMA-HDCC 3

Syntheses of N-[(2-hydroxy-3-dimethyl dodecylammonium) propyl] chitosan chloride

(HDCC)

and

O-acrylamidomethyl-N-[(2-hydroxy-3-dimethyl

dodecyl

ammonium) propyl] chitosan chloride (NMA-HDCC) were conducted following the procedures reported in literature [19]. Scheme 1 shows the reactions for synthesizing the novel chitosan derivatives. The first step was to synthesize an epoxypropyl dodecyl dimethyl quaternary ammonium salt. N,N-Dimethyldodecylamine (10g) was added in n-propanol (15mL), and continuously stirred for 1 h at 50oC. Then, epichlorohydrin (5g) was added to the reaction mixture slowly in the following 3 h. The mixture was left to react for 10 hours at 50℃. At last, the reaction mixture was then vacuum distilled and precipitated with ether at room temperature. A white gel-like epoxypropyl dodecyl dimethyl quaternary ammonium salt was dried at 20℃ under vacuum overnight. The second step was the synthesis of HDCC with epoxypropyl dodecyl dimethyl quaternary ammonium salt and chitosan. Deacetylated chitosan (2g) was dispersed in distilled water (20mL) and n-propanol (10mL) at 85℃ while stirring for 1 hour. Then NaOH (mass fraction was 40%) was added to the reacting system slowly. At the same time, epoxypropyl dodecyl dimethyl quaternary ammonium salt (4g) was added in four portions at 1h intervals. The reaction solution became yellowish and clear after 48 h of reaction. Hydrochloride was added into reaction solution to adjust pH. Then the mixture was filtered and the liquid was precipitated with cold acetone. The yellowish productHDCC was filtrated and then further purified by a Soxhlet extractor in ethanol for one day. Then the obtained product was dried at 80 ℃ under vacuum. At last, the dried HDCC (3g) and N-methylolacrylamide (7.2g) were dissolved in distilled water containing 4-methoxyphenol (0.03g) as a polymerization inhibitor, then NH4Cl (1.53g) was added and dissolved. The solution was kept 130 ℃, 10 min. After reaction procedure, methanol (45mL) was added into the mixture. The crude substance was obtained by precipitation method in acetone solvent (200mL). The product was washed thoroughly with a mixture of 1:1 acetone–ethanol and finally with ether. The obtained white product was dried at 40℃ under vacuum for 2 days [19]. Structures of samples were characterized with FTIR and nuclear magnetic resonance 4

(NMR). FTIR was measured by a Nicolet AT-380 spectrometer using potassium bromide pellets, with acquisition conditions of spectral width at 4000-400 cm-1, resolution at 4 cm-1, and 32 accumulations. 1H-NMR spectra of chitosan and its derivatives dissolved in 0.5mL of DOH were recorded on a Bruker AV 400 (400 MHz) spectrometer. The solubility of chitosan and its derivatives was assessed in distilled water. NMAHDCC (0.4g) was put into a beaker, then, water was added until the sample was completely dissolved. The solubility of product (the max quantity of NMA-HDCC which can be dissolved in 100g of water) was calculated as followings [19]. S = m / M × 100 Where, S is the solubility of NMA-HDCC in aqueous solution; m is the max quantity of NMA- HDCC in aqueous solution and M is the total mass of water. The analytical method of the degree of substitution of the product was based on the procedure of Lim[4]. 2.3 Treatment of fabrics by chitosan and chitosan derivatives Chitosan and its deratives were dissolved in distilled water at a concentration of 1% owb respectively. In addition, 1% acetic acid was added in chitosan bath to improve the solubility of chitosan and NaHCO3(20g/L) was put into the bath of NMA-HTCC and NMA-HDCC to keep the proper reactive condition. Cotton fabrics were padded with finishing agent (chitosan and its derivatives) using a laboratory padder at 85% wet pick up. The cotton samples treated by chitosan, HTCC and HDCC were dried at 70℃ for 5 min, and the samples treated with the NMA-HTCC and NMA-HDCC were cured at 140 ℃ for 3 min. All treated fabrics were washed with water, air-dried for antimicrobial test and dyeing process [20]. 2.4 Antimicrobial properties of fabrics Antimicrobial properties of samples were evaluated according to the standard of AATCC 100-1999. E. coli was the testing organism. The fresh E. coli in nutrient broth was diluted to a final concentration of 1.0 × 105 CFU/mL with sterilized distilled water. This diluted organism solution was the working bacterial dilution

[4].

A round shape

cotton fabric (1g) and 1 mL of the working bacterial dilution were put into a 250 mL

5

Erlenmeyer flask. All flasks were capped loosely, then shaken for 12h at 37℃ and 150 rpm using an incubator shaker. After the contact procedure ended, the distilled water was used to dilute the bacterial solution. 1 mL of the diluted bacterial solution was inoculated in nutrient agar and then incubated at 37℃ for 24h. The number of surviving cells can be counted after inoculation and then convert to CFU/mL by formula calculation. The antimicrobial property of chitosan and its derivatives was expressed in terms of the percentage reduction of the organism after contact with the test specimen compared to the control. The percentage reduction was calculated using the following equation [4]: Reduction%= [(B – A)/ B]*100% Where, A is the surviving cells (CFU/mL) for the flasks containing test samples (cotton fabrics treated by chitosan and its derivatives) after contact time; B is the surviving cells (CFU/mL) for the flasks containing blank cotton fabric sample (untreated cotton fabric) after contact time. 2.5 Durability of fabrics treated with chitosan and the chitosan derivatives The durability of the chitosan derivatives on the fabrics was evaluated by a home washing machine at medium setting after repeated launderings. The shape and size of the fabric was the same as the tested one. All fabrics were subjected to thirty consecutive launderings with a detergent

[9],

then rinsed with running water and air-dried after the

washing process. The anti-bacterial test of fabrics after thirty launderings was conducted following the same method. 2.6 Dyeing and soap washing methods The dyeing process was carried out using exhaustion method at 2% (owf) shade with material to liquor ratio 1:30 in water bath. Sodium chloride (50 g/l) and sodium carbonate (20 g/l) were used as exhaustion agent and fixation agent in dyeing process, respectively. All fabrics were soaked in water several minutes before the dyeing procedure. Dyeing processes for different dyes (C.I. Reactive Red 2 and C.I. Reactive Black 5) in this experiment are presented below. A prepared fabric (pretreated with chitosan or its deratives, detailed treatment conditions follow the paragraph of Treatment of fabrics by chitosan and chitosan derivatives in experimental section) was dipped in the dye bath for

6

1 h, then thoroughly washed with water several times and dried. The salt-free reactive dyeing process was the same as followings, except not adding salt in the dyeing solution. The soap washing process was carried out in a solution containing 5 g/L of a detergent. The fabric was dipped in the solution (material to liquor ratio 1:50) at 95-100 ℃ for 10 min. After that procedure, the cotton fabric was rinsed under running water, and then dried at a proper temperature. 1) C.I. Reactive Red 2 Dyes, fabric

30℃

15min

NaCl

Na2CO3

15min

30min

Washing, soap washing, washing, drying

2) C.I. Reactive Black 5 Na2CO3 Dye, fabric

40℃

15min

NaCl

15min

30min 60oC Washing, soap washing, washing, drying

2.7 Whiteness measurement of fabric pretreated with chitosan and novel chitosan Whiteness measurement was operated by WSB-Ⅱwhiteness meter. Cotton sample was folded four times and measured at three different positions. The average value of the CIE Whiteness Index was calculated and recorded in this experiment. m2.8 Dyeing properties of fabrics pretreated with chitosan and chitosan derivatives The dye uptake was expressed by comparing concentration of dye in bath before and after dyeing procedure. The concentration of dye can be got using spectrophotometer machine and calibration curve of dye [20]. The exhaustion rate (Ex) and fixation rate (Fx) were calculated with the absorbency of different dyeing process. The calculation expressions are as below: Ex=[(A－B)/A]×100% Fx =[Ex－D/C]×100% Where, A is the absorbency of a dye before dyeing; B is the absorbency of the 7

residual liquid after dyeing. C is the absorbency of the standard soaping liquid; D is the absorbency of the residual liquid after soaping. Color measurement of sample was characterized by measuring K/S values using an SF 650 PSUS color measuring equipment under D65 Illuminant and 10°observer conditions [18]. Washing fastness tests were performed according to AATCC 61-2003 (3A) using the Rapid HB-4H6F washing fastness tester. Rubbing fastness tests were performed according to AATCC 8-2004 using the AATCC CROCKMETER rubbing fastness tester. 3. Results and discussions 3.2 Water solubility The solubility of NMA-HDCC in water is 5.21 g at neutral conditions and a little lower in alkaline media. The solubility of chitosan in acidic media is high but is very low in water under neutral or alkaline condition. The water solubility was improved by the incorporation of the quaternary ammonium salt group into its backbone of chitosan. NMA-HDCC becomes soluble in both neutral and alkaline media. It is desirable to make chitosan and its derivatives soluble under alkaline since cotton fabrics can be treated under such a condition [3]. 3.3 The degree of substitution of the product The degree of substitution of the product obtained from three parallel experiments is 0.603. The lower value mainly because the degree of deacetylation of chitosan is insufficient; besides, as raw material of second step, the dodecyl dimethyl quaternary ammonium salt containing impurity decreased the epoxy content, which affect the substitution reaction. 3.4 Antibacterial properties of fabrics Table 1 showed the bacteria inhibitory rates of cotton fabrics treated with chitosan and its derivatives. As a comparison, two similar chitosan derivatives, N-[(2-hydroxy-3trimethylammonium) propyl] chitosan chloride (HTCC) and O-acrylamidomethyl-N-[(2hydroxy-3-trimethylammonium) propyl] chitosan chloride (NMA-HTCC)[20], were also employed in the antimicrobial tests. The results revealed that the treated fabrics

8

demonstrated antimicrobial properties. Chitosan is a natural polymer with limited antimicrobial properties confirmed. HTCC, NMA-HTCC, HDCC, and NMA-HDCC are quaternary ammonium salts which are biocides. The results showed that the antimicrobial activity of fabric treated with chitosan was weaker than the ones treated by the chitosan derivatives, and the fabrics treated with NMA-HDCC and NMA-HTCC showed better antimicrobial activities with almost 100% reduction. Table 1 Antibacterial property of cotton fibers treated with different agents Bacteria Reduction (%) Treated fabrics Before 30 launderings

after 30 launderings

Chitosan treated fabric

95.1

Weak

HTCC treated fabric

96.2

weak

HDCC treated fabric

97.9

weak

NMA-HTCC treated fabric

99.0

82.9

NMA-HDCC treated fabric

99.3

85.3

Note: HTCC and NMA-HTCC were prepared according to the method of Sang-Hoon Lim[9]。

Chitosan does not form chemical bonds with cellulose and is thus held on cotton only by the numerous hydrogen bonds and Van der Walls forces of attraction[18]. HTCC and HDCC could not form covalent bonds with cellulose as well. However, both NMAHTCC and NMA-HDCC possess vinyl groups that can react with cellulose. The antibacterial properties of the fabrics could survive 30 times of repeated launderings, proving the durability of both NMA-HTCC and NMA-HDCC treated fabrics (Table 1). These data also indicate that NMA-HDCC formed chemical bonds with cellulose fabrics, and thus NMA-HDCC treated fabric are durable against repeated launderings. Both HDCC and NMA-HDCC contain an alkyl chain, dodecyl group, much longer than the methyl group in HTCC and NMA-HTCC compounds. Generally speaking quaternary ammonium salts with longer alkyl chains could demonstrate better antimicrobial functions that the ones without the long chains. 9

The results in Table 1

show some consistence with the general rule, suggesting that HDCC structure is advantageous than HTCC series. 3.5 Whiteness of cotton fabrics treated with chitosan and its derivatives Cellulose can be degraded by heat of curing chemicals, and this process involved oxidation reaction and chain scission of the polymer. The resulted aldehyde groups in degradation reaction could interact with cellulose and cause yellowing observed on the treated fabrics. If alkali and chemicals existed in fabric, the yellowing effect would be further enhanced. The procedure of treating cotton fabrics with NMA-HDCC here involved both heat and alkali, further more, the color of finishing agent was yellow. Therefore, the whiteness value of the NMA-HDCC treated fabric decreased significantly, which could be an issue affecting the applications, as shown in Table 2. Table 2 Whiteness values of treated cotton fabrics fabrics

Whiteness values

Untreated fabric

78.1

Fabric treated with chitosan

74.4

Fabric treated with HDCC

70.8

Fabric treated with NMA-HDCC

67.1

3.6 Dyeing properties of fabrics The quaternary ammonium salt structures incorporated onto cellulose will bring in cationic ions onto the polymer, and thus the products will become more interactive with anionic species. Such a feature can be employed in assisting incorporation of anionic dye molecules, such as reactive dyes, to cellulose. Figure 5 shows the exhaustion curves of a reactive dye (C. I. Reactive Red 2) on fabric. The dye uptake results of the dyeing processes revealed that the untreated cotton samples exhausted lowest amount of reactive dyes, with the exhaustion curve at the bottom. The fabrics treated by chitosan (CTS), HDCC, and NMA-HDCC all demonstrated increased exhaustion of the dye without addition of sodium chloride, an electrolyte, in the dyeing bath, proving feasibility of socalled salt-free dyeing of the treated fabrics. Comparing to the chitosan treated sample,

10

the HDCC and NMA-HDCC treated fabrics exhibited higher exhaustion values due to the positive charges carried by the quaternary ammonium salt groups on chitosan derivatives. The exhaustion rate of the reactive dye on the chitosan treated samples was lower in general. However, all dye uptake values were lower than those dyed with sodium chloride added, indicating that there was still a gap between the fabric treatments and conventional process in reactive dyeing.

Figure 5 Exhaustion curves of C.I. Reactive Red 2 on cotton fabrics (Detailed treatment conditions follow the paragraph of Treatment of fabrics by chitosan and chitosan derivatives in experimental section)

The final exhaustions and fixations of two reactive dyes on cotton fabrics are presented in Tables 3 and 4. Both dyes showed increased dye fixation rates on the treated cotton than that on the untreated sample, but the highest one was achieved on the cotton fabric samples dyed by the conventional method (with salt). The presence of positive charge on the HDCC and NMA-HDCC treated fabric samples neutralize partial negative charges of the wet cellulose fibers and reduce the ξ potential on the surface of the fabric, so the ionic repulsion between the wet fibers and the dye was reduced during the dyeing process. However the power of the cationic groups on the fibers was still weaker than the effect of electrolyte of sodium chloride. Table 3 Results of dyeing property treated cotton with C.I. Reactive Red 2 Dyeing process

Dye uptake

11

Fixation rate

Salt-added

Salt-free dyeing

Untreated fabric

75.09%

57.31%

Untreated fabric

61.42%

38.28%

Treated with Chitosan

64.90%

53.46%

Treated with HDCC

67.28%

52.97%

Treated with NMA-HDCC

66.87%

54.49%

Table 4 Results of dyeing treated cotton with C.I. Reactive Black 5 Dyeing process Salt-added

Salt-free dyeing

Dye uptake

Fixation rate

Untreated fabric

77.91%

62.31%

Untreated fabric

63.79%

52.37%

treated with CTS

69.17%

58.87%

treated with HDCC

73.12%

61.06%

treated with NMA-HDCC

76.81%

61.23%

K/S values can represent the dye concentrations of the color fabrics. Figure 6 shows K/S values of the dyed samples, which also reflect the color strength of fabrics pretreated with novel chitosan and original cotton samples. The cotton samples were dyed with 2% o.w.f C.I. Reactive Red 2 or Black KN-B in the absence or the presence of sodium chloride and alkali. Generally, it is easy to dye cotton fabric in light and dark shades, but difficult to get color with deep and bright shade. Since cotton fabric has been cationized by chitosan deravatives, the dyeing behavior of the treated fabric changed as well. Figure 6 clearly proved that the color strength of the cotton sample pretreated with NMA-HDCC and HDCC were much higher than that of the untreated one in the absence of the salt. Therefore, if the cotton fabrics were grafted with the quaternary ammonium salt derivative, the K/S value would be improved without addition of salt, which could be economically advantageous.

12

Figure 6 K/S values of fabrics dyed by C.I. Reactive Red 2 and C.I. Reactive Black 5

The washing fastness of the dyed samples can be observed from Table 5. The washing fastness of the cotton samples pretreated with NMA-HDCC showed higher colorfastness grade compared with the others. The washing fastness of the dye is dependent on the bonding between the dye and the finishing agent as well as the bonding between the finishing agent and cellulose[18]. For NMA-HDCC, the ionic bond between anionic dyes and the positive charges on the quaternized groups and the covalent bond between NMA-HDCC and hydroxyl groups in the cellulose improved the washing fastness of dyes on cotton. The washing fastness of the fabric pretreated with HDCC was the lowest one among the treated fabrics, this was mainly because its molecule has good solubility in water due to its ionic structure. The rubbing fastness of the color samples (Table 6) presented the same trend as the washing fastness. Table 5. Washing fastness of dyed cotton fabrics color fastness to washing/grade(AATCC)

Dyeing process

C.I. Reactive Black 5

C.I. Reactive Red 2

Stained on

Stained on

Stained on

Stained

cotton

wool

cotton

wool

Salt-free and untreated

4

4~5

2

4~5

Salt added and untreated

4

4~5

2~3

4~5

Salt-free and treated with Chitosan

4

4~5

2~3

4~5

13

on

Salt-free and treated with HDCC

4

4~5

3

4~5

Salt-free and treated with NMA-HDCC

4

5

3

4~5

Table 6. Rubbing fastness of dyed cotton fabrics Rubbing fastness/grade( AATCC) C.I. Reactive Black 5

C.I. Reactive Red 2

Dyeing process dry

wet

dry

wet

Salt-free and untreated

5

4~5

4~5

4~5

Salt added and untreated

5

4

5

4

Salt-free and treated with Chitosan

4~5

4

4~5

4

Salt-free and treated with HDCC

4~5

4

5

3~4

Salt-free and treated with NMA-HDCC

5

4~5

5

4

4. Conclusions A water soluble chitosan derivative O-acrylamidomethyl-N-[(2-hydroxy-3dodecylammonium)propyl] chitosan chloride (NMA-HDCC), was synthesized and applied to cotton samples with a pad-dry-cure process, and the treated fabrics were tested for antimicrobial and dyeing properties. The NMA-HDCC treated fabrics showed powerful and durable antimicrobial properties against E. coli even after 30 home launderings. In addition, salt-free reactive dyeing of the cotton pretreated with NMAHDCC showed good dyeing properties and washing fastness. The results suggested the new chitosan derivative can be a potential functional auxiliary for textile dyeing and finishing. References [1] A. Crosio, B. E. Fornasari, G. Gambarotta, et al., Neural Regeneration Research 14(2019) 1079-1084. [2] K. Shao, B. Q. Han, W. Dong, Journal of Ocean University of China 14(2015) 88814

896. [3] H. B. Benjamin ， M. Yildirim-Aksoy ， C. A. Shoemaker ， et al., Journal of Fish Diseases 42(2019) 371-377. [4] S. H. Lim, S. M. Hudson, Carbohydrate Polymers, 56(2004) 227-234. [5] T. Lou, X.Yan, X.J. Wang, International Journal of Biological Macromolecules 135 (2019)919-925. [6] C. Hua, R. H. Zhang, F. Bai, et al., Chinese Journal of Chemical Engineering 25(2017) 153-158. [7] W. Zhang, X. L. Dai , J. J. Zhou , et al., Textile Auxiliaries 33(2016) 47-51. [8] T. Zhao, G. Sun, X. Y. Song, Journal of Applied Polymer Science 108(2008) 19171923. [9] S. H. Lim, S. M. Hudson, Carbohydrate Research 339(2004) 313-319. [10] Rejane C. Goy, Sinara T. B. Morais, Odilio B. G. Assis, Revista Brasileira de Farmacognosia 26(2016)122-127 [11] P. Opanasopit, M. Petchsangsai, T. Rojanarata, T. Ngawhirunpat, W.Sajomsang, U. Ruktanonchai, Carbohydrate Polymers 75(2009) 143-149. [12] Nadia A. Mohamed, Magdy W.Sabaa, Ahmed H.El-Ghandour, International Journal of Biological Macromolecules 60(2013)156-164. [13] R. O. Pedro, M. Takaki, T. C. C. Gorayeb, et al., Microbiologica Research 168(2013)50-55. [14] A. Verlee, S. Mincke, C. V. Stevens, Carbohydrate Polymers 164(2017) 268-283. [15] M., Wu, Z. Long, H. Xiao, C. Dong, Carbohydrate Research 434(2016)27-32. [16] P. J. Dong, J. B. Luo, Paper and Paper Making 37(2018) 21-23. [17] J. M. Jiang , Z. X. Li , L. Shen , et al., Polymer Materials Science and Engineering 29(2013) 20-27. [18] D. Gupta, A. Haile, Carbohydrate Polymers 69(2007) 164-171. [19] T. Xu, M. H. Xin, M. C. Li, H. L. Huang, S. Q. Zhou, Carbohydrate Polymers, 81(2010) 931-936. [20] Nadeeka D.Tissera, Ruchira N. Wijesena, K. M. Nalinde Silva, Ultrasonics Sonochemistry 29(2016)270-278. 15