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Incorporation of poly(3-acrylamidopropyl trimethylammonium chloride-co-acrylic acid) branches for good sizing properties and easy desizing from sized cotton warps

  • Chaohui Zhang , Wei Li EMAIL logo and Zhenzhen Xu
Published/Copyright: February 24, 2023
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e-Polymers
From the journal e-Polymers Volume 23 Issue 1

Abstract

This study aimed to ascertain the influence of poly(3-acrylamidopropyl trimethylammonium chloride-co-acrylic acid) [P(ATC-co-AA)] on the adhesion, film properties, desizability of cornstarch, and reveal a suitable mole percentage of ATC units on the P(ATC-co-AA) for acquiring a new starch-based size [S-g-P(ATC-co-AA)]. A series of S-g-P(ATC-co-AA) samples were synthesized by the graft polymerization of acid-converted cornstarch with ATC and AA monomers. Their adhesion, film properties, and desizability were assessed. The results displayed that the P(ATC-co-AA) branches could significantly improve the adhesion to cotton fibers and diminish the film brittleness of starch. Under similar grafting ratio, the adhesion and desizability of S-g-P(ATC-co-AA) depended on the mole percentage of ATC units. Increasing the percentage favored the adhesion but disfavored the desizability. The percentage displayed a low effect on the film properties. S-g-P(ATC-co-AA) with a mole percentage of 57.7% presented good sizing properties and easy desizing, which had potential application in cotton warp sizing.

Keywords: cornstarch; graft polymerization; adhesion; film properties; desizability

1 Introduction

Nowadays, the rapid development of the world economy has brought about increasing environmental pollution. As a result, starch, a renewable (1), low-cost (2,3), and environment-friendly polymer material, is highly praised by people and widely used in the field of warp sizing. However, the cyclic structure and numerous hydroxyl groups in the starch molecules, impart the starch with inadequate adhesion and high film brittleness (4). In the warp sizing, the adhesion of textile size to fibers exerts the functions of strengthening warp strength by gluing the fibers together as well as reducing the protruding hairs on the warp surface (5). The film on the warp surfaces formed from size paste provides a protection for the warps from various abrasions, thereby facilitating the weavability of warps (6). Therefore, the inadequate bonding and high film brittleness will seriously restrict the usability of starch in the warp sizing, which cannot meet the requirements of warp sizing. As a result, starting from the relationship between the structure and properties of starch macromolecules, it is of great significance to the innovation of key technology of textile sizing via the research and development of new starch size with good adhesion and film properties.

Grafted starch is a kind of starch derivative prepared by the graft polymerization of starch with vinyl monomers. Graft polymerization has been considered as an efficient means to change the molecular structure of starch (1,7), and to improve its sizing properties (8). Starch graft polymers have been partially used in the warp sizing (9) and papermaking (10). Recently, the monomers utilized in the graft polymerization mainly comprise the most common acrylic acid (AA) (11), 2-acryloyloxyethyl trimethylammonium chloride (12), and so forth, for enhancing the sizing properties of starch-based sizes. Nevertheless, the incorporation of negatively charged AA units will induce electrostatic repulsion with cotton fibers (present negative zeta potential in water) at the layer–fiber interface, which is not conducive to the adhesion of starch to cotton fibers. In contrast, cationic grafted starch such as starch-g-poly(3-acrylamidopropyl trimethylammonium chloride) [S-g-P(ATC)] prepared by the grafting reaction of starch with ATC monomer, can produce electrostatic attraction at the layer–fiber interface, which favors the adhesion, but the attraction will increase the difficulty of starch desized from sized cotton warps, leading to the probability of occurrence of incomplete desizing. Therefore, in this study, the AA and ATC monomers were selected to modify starch for introducing the P(ATC-co-AA) branches simultaneously containing the ATC and AA units, and thus strong adhesion and film properties as well as easy desizing might be expected by the combination of the two units on the P(ATC-co-AA) branches. The modification, that is, the graft polymerization of acid-converted starch (ACS) with the ATC and AA monomers, was conducted in an aqueous phase using Fe2+-H2O2 initiator for the preparation of S-g-P(ATC-co-AA), as presented in Figure 1.

Figure 1 The preparation of S-g-P(ATC-co-AA) by graft polymerization of starch with ATC and AA using Fe2+-H2O2 initiator.
Figure 1

The preparation of S-g-P(ATC-co-AA) by graft polymerization of starch with ATC and AA using Fe2+-H2O2 initiator.

Currently, no study has been carried out to estimate the potential application of S-g-P(ATC-co-AA) in the cotton warp sizing. There was no investigation about the effects of P(ATC-co-AA) branches upon the adhesion to cotton fibers, film properties, and desizability, particularly no study to reveal the suitable mole percentage of ATC units incorporated on the P(ATC-co-AA) branches. Accordingly, one objective of this study was to examine the influence of P(ATC-co-AA) branches on the properties of starch. Another aim of this study was to investigate the influence of mole percentage of the ATC units on the branches upon the properties of S-g-P(ATC-co-AA) for achieving a suitable of mole percentage to impart the S-g-P(ATC-co-AA) with good adhesion to cotton fibers and film properties as well as easy desizing, simultaneously. To fulfill these objectives, granular S-g-P(ATC-co-AA) with similar grafting ratio and control ACS were synthesized in the heterogeneous aqueous phase. The samples and their films were chemically characterized. Moreover, the adhesion of S-g-P(ATC-co-AA) samples to cotton fibers, film properties, and desizability were investigated using ACS as a control sample. This study might supply a new, high-performance, amphoteric starch graft polymer product for promoting the application of starch-based sizes in the cotton warp sizing.

2 Experimental section

2.1 Materials and reagents

Native cornstarch with a paste viscosity of 48 mPa·s was purchased from Shandong Hengren Industry and Trade Co., Ltd (Shandong Province, China). The ATC (75 wt%) was obtained from TCI Shanghai (Shanghai, China). The other analytically pure chemicals, such as H2O2 with a mass concentration of 30%, AA, HCl, (NH4)2Fe(SO4)2, hydroquinone, NaOH, and H2SO4, were supplied by Sinopharm Chemical Reagent Co., Ltd (Shanghai, China). Pure cotton roving (372 tex) was kindly supplied by Huamao Textile Co., Ltd (Anhui Province, China).

2.2 Synthesis of S-g-P(ATC-co-AA) samples

Before synthesis, refinement of the native cornstarch with methanol–distilled water mixture (85/15 v/v) at 40°C and further acid-conversion with 2 M hydrochloric acid (27 mL) at 50°C for 3 h were conducted to dislodge the proteins and lower its viscosity to 10 mPa·s (13,14), respectively.

The ACS was utilized to synthesize the S-g-P(ATC-co-AA) sample by the graft polymerization of the ACS with ATC and AA monomers in an aqueous phase using a redox system, as depicted in Figure 1. In detail, the dried ACS (120 g) was added to distilled water to prepare a 30 wt% aqueous dispersion, which was transferred into a 1,000 mL four-necked flask, adjusted its pH to 3–4 with dilute HCl, and heated to 30°C under consistent agitation. After removing the air in the reaction system with nitrogen gas for 0.5 h, 28 mL of 0.5 wt% (NH4)2Fe(SO4)2 aqueous solution, 30 mL of 1.0 wt% H2O2 aqueous solution, ATC, and AA were added dropwise for 30–40 min. After the addition, the mixture was constantly stirred, kept at 30°C, and reacted for 3 h under a nitrogen atmosphere. Then, 1 mL of hydroquinone solution (2 wt%) was added to stop the reaction. The reaction system was neutralized to pH 6.5–7 with a 2 wt% NaOH solution, and then filtered, washed, oven-dried, ground, and sieved to obtain the powdered S-g-P(ATC-co-AA) sample.

2.3 Characterization of S-g-P(ATC-co-AA)

The spectra of ACS and S-g-P(ATC-co-AA) samples were analyzed on a Nicolet Nexus 470 Fourier transform infrared (FTIR) spectrophotometer (Thermo Electron Corporation, Massachusetts, USA) for revealing the successful incorporation of the P(ATC-co-AA) branches on the backbones of starch. Prior to the analysis, the sample was mixed with anhydrous KBr, and pressed into disk-shaped pellet. The wavenumber ranged from 500 to 4,000 cm−1.

The homopolymer within the grafted starch sample should be got rid of. The homopolymer P(ATC-co-AA) within S-g-P(ATC-co-AA) was fully removed by the treatment of washing with distilled water five times according to the study (15).

Conversion of monomer to polymer (%) represents a weight percentage of the converted monomers to the total monomers added in the grafting reaction, which is measured according to the study (16) on the basis of the titration of double bonds of residual monomers in the filtrate, and calculated using Eq. 1 as follows:

(1) C m = W 1 − W 0 W 1 × 100 %

where W 0 and W 1 correspond to the weights of residual and added monomers, respectively.

In general, the grafting ratio, as a mass ratio of the monomer units to the starch substrate, is used to indicate the level of starch graft polymerization (17). Grafting ratio of the S-g-P(ATC-co-AA) sample was acquired by measuring its nitrogen content using Kjeldahl method (18), as well as its carboxyl content with a titration method (19). Grafting ratio (R g, %) and grafting efficiency (E g, %) were calculated using Eqs. 2 and 3 as follows:

(2) R g = C n × 7.377 + 1.6 C c 1 − ( C n × 7.377 + 1.6 C c ) × 100%

(3) E g = W 2 W 1 − W 0 × 100 %

where C n and C c denote the nitrogen content of the sample and its carboxyl content, respectively, and W 2 indicates the weight of P(ATC-co-AA) branches grafted onto the starch chains.

2.4 Determination of bonding force

A standard method (FZ/T 15001-2008) in China was utilized to determine the adhesion of starch sample to fibers. In detail, the S-g-P(ATC-co-AA) or ACS (used as a control) sample was added and stirred in distilled water, followed by complete gelatinization at 95°C for 1 h under subsequent agitation to form a 1 wt% aqueous paste. The paste was then transferred into a metal box which had been stored in a water bath at 95°C. A steel frame, onto which the roving had been carefully wound, was impregnated with the paste for 5 min. After drying in air, the sized roving was equilibrated at 65% relative humidity (RH) and 20°C for 24 h, and then conducted a tensile test until failure to obtain the bonding force of sized roving for denoting the adhesion of S-g-P(ATC-co-AA) or ACS to fibers. The tensile test was carried out on a YG026D Electronic Strength Tester (Ningbo Textile Instrument Factory, China) according to the study (20). The data reported were the mean values of 20 parallel tests with which the abnormal results had been rejected.

2.5 Determination of zeta potential

Starch sample was added and stirred in distilled water to form a 0.1 wt% mixture which was pasted by heating the mixture to 95°C and stirring for 1 h. When the paste was cooled to room temperature, determination of the zeta potential of the formed 0.1 wt% starch paste was conducted in duplicate on a Malvern Zetasizer Nano-ZS90 (Malvern Instrument Inc., UK) and the average was reported.

2.6 Determination of starch film

Thin film of S-g-P(ATC-co-AA) or ACS sample was made by a casting method with 6 wt% aqueous paste of the sample (21). The film was cut into 200 mm × 10 mm strips for the subsequent property determination.

After storage at 20°C and 65% RH for 24 h, the thicknesses of the strips were tested using an YG141 Thickness Gauge (Changzhou Textile Electronic Tester Co., Ltd, China). Then, their tensile strengths and elongations at break were tested with the YG026D Electronic Strength Tester. For each set of data, 20 parallel tests were implemented and the averages were reported. The measurement of moisture regain was performed in duplicate per film sample by determining the weight loss of the film after drying in a vacuum oven at 105°C according to our previous study (20).

An X-ray diffractometer (XRD-6000, Shimadzu Co., Japan), with Cu-Kα radiation at 30 mA and 40 kV, was utilized to perform the X-ray diffraction (XRD) analysis of ACS and S-g-P(ATC-co-AA) films. The Bragg angles (2θ) were in the range of 5–40°, and the scanning speed was 4°·min−1.

2.7 Hank sizing and desizing

The hank sizing of cotton warps was conducted using the procedure reported previously (4). The procedure mainly contains the following steps: (i) preparing a 6 wt% starch aqueous paste using the method in the viscosity determination, and (ii) immersing the cotton warps (3 g) in hanks in the prepared paste for 20 min and extruding the immersed warps to dislodge the redundant paste on warps; and (iii) drying in air to acquire the sized warp sample.

Desizability of the starch was estimated by an oxidant desizing method, which was carried out by boiling sized warps in a desizing liquid (liquor ratio of 1:50) for 0.5 h. The dosages of chemicals were 2 g·L−1 NaOH, 4 mL·L−1 H2O2, and 2 g·L−1 JFC (as penetrating agent) in the liquid. The boiled warps were followed by washing with hot distilled water three times to remove the degraded starch, and oven-drying to obtain the dry weight. Desizing efficiency (E d, %) was calculated using Eq. 4 as follows:

(4) E d = m 2 − m 3 m 2 − m 1 × 100 %

where m 1, m 2, and m 3 indicate the dry weights of unsized, sized, and desized cotton warps, respectively.

Starch add-on of sized warps was measured by an acid-desizing method (22). The sized warps were boiled in dilute H2SO4 to degrade the starch on the warps, and then the degraded starch products were washed away using hot distilled water. Meanwhile, an iodine test was conducted to check if the starch had been completely removed from the warps.

3 Results and discussion

3.1 Characterization

The FTIR spectra collected in the region of 500–4,000 cm−1 were utilized to confirm the successful incorporation of grafted P(ATC-co-AA) branches on the ACS molecules, as shown in Figure 2. The peaks at the wavenumbers of 2,928 cm−1 in the spectrum of ACS (curve a) and 2,930 cm−1 in the spectrum of S-g-P(ATC-co-AA) (curve b) corresponded to the asymmetric stretching vibration peak of C–H. The peak presented at 1,420 cm−1 was attributed to the absorption peak of the –CH2 group. The peak at 1,157 cm−1 was ascribed to the C–O bond stretching vibration peak (23). In the addition of the characteristic absorption peaks of the ACS, there were three new peaks in the spectrum of the S-g-P(ATC-co-AA). Two peaks observed at the wavenumbers of 1,641 and 1,481 cm−1 corresponded to the characteristic absorption bands of C═O (24) and C–N (25) in the ATC units. Besides, one new peak presented a 1,570 cm−1 in the spectrum of the S-g-P(ATC-co-AA) corresponded to the characteristic absorption band of carboxylate (26) in the AA units. The three peaks concluded the existence of P(ATC-co-AA) branches on the starch molecules.

Figure 2 FTIR spectra of the granular ACS (a) and S-g-P(ATC-co-AA) (b) films at grafting ratio = 6.96%.
Figure 2

FTIR spectra of the granular ACS (a) and S-g-P(ATC-co-AA) (b) films at grafting ratio = 6.96%.

In this study, a fixed mass percentage of both ATC and AA monomers to ACS sample for synthesizing the S-g-P(ATC-co-AA) samples was 15 wt%, while the molar ratios of ATC to AA were in the range of 20/80 to 80/20 during the grafting reactions. Grafting parameters of the branch-grafted starches (S-g-P(ATC-co-AA)) synthesized are determined and displayed in Table 1. As shown in Table 1, the conversions of monomers to synthetic polymers were all over 93% and just had a slight change with the variation in the molar ratio. This observation confirmed that most of the monomers charged into the reaction system had participated in graft polymerization and converted into synthetic polymers. As the molar ratios changed from 20/80 to 80/20, the mole percentage of ATC units determined on the P(ATC-co-AA) branches varied from 19.0% to 77.9%. The grafting ratios and efficiencies of all S-g-P(ATC-co-AA) samples were approximately 7.00% and 50.0%, respectively, and also had no obvious difference as the molar ratio of ATC to AA increased. These similar grafting ratios enabled us to perform the study about the effect of the mole percentage of ATC units on the grafted P(ATC-co-AA) branches upon the adhesion, film properties, and desizability of S-g-P(ATC-co-AA) once the influence of the grafting ratio had been substantially eliminated.

Table 1

Grafting parameters of the synthesized S-g-P(ATC-co-AA) samples

Starches Molar ratio of ATC to AA (%) Mole percentage of ATC units determined on grafted branches (%) Conversion of monomers to polymers (%) Grafting efficiency (%) Grafting ratio (%)
S-g-P(ATC-co-AA) 20/80 19.0 95.2 50.5 7.22
40/60 38.1 94.9 49.7 7.08
60/40 57.7 94.5 49.1 6.96
80/20 77.9 94.1 48.6 6.86

3.2 Influence of the mole percentage of ATC units on the P(ATC-co-AA) branches on the adhesion to fibers

Under the similar grafting ratio, the influence of the mole percentage of ATC units on the P(ATC-co-AA) branches upon the adhesion of starch to cotton fibers was evaluated, as exhibited in Figure 3. As seen, the bonding force of ACS (mole percentage = 0) to cotton fibers was 63.9 N. The S-g-P(ATC-co-AA) was stronger than ACS in the bonding force to cotton fibers, which indicated that incorporating the grafted P(ATC-co-AA) branches could enhance the adhesion of starch to cotton fibers. The adhesion of S-g-P(ATC-co-AA) to the fibers was closely related to the mole percentage of ATC units. When the mole percentage increased from 19.0% to 77.9%, the bonding forces of S-g-P(ATC-co-AA) to cotton fibers got consistent promotion, which suggested that a gradually promoted adhesion to cotton fibers for S-g-P(ATC-co-AA) was exhibited as the mole percentage increased.

Figure 3 Influence of the mole percentage of ATC units on the P(ATC-co-AA) branches on the adhesion to cotton fibers.
Figure 3

Influence of the mole percentage of ATC units on the P(ATC-co-AA) branches on the adhesion to cotton fibers.

On the basis of the fracture location, the fracture of an adhesive joint can be generally divided into cohesive and interfacial failures (27). The former corresponds to the failure that happens inside of the matrix of an adhesive layer, which is closely in correlation with the strength of adhesive layer; and the interfacial failure is commonly generated at the layer–fiber interface, which is commonly dependent on the interfacial attraction at the interface.

In this study, the ATC and AA units on the P(ATC-co-AA) branches are cationic and anionic, respectively. Accordingly, the effect of the mole percentage on the zeta potential of S-g-P(ATC-co-AA) samples is investigated, and the results are illustrated in Table 2. As observed, the potential of S-g-P(ATC-co-AA) samples depended on the mole percentage of ATC units on the branches. And it presented a linear relationship between the potential and mole percentage. With the increase in the mole percentage from 19.0% to 77.9%, the potential varied from −14.8 to +18.2 mV. It has been revealed that the electrostatic attraction produced at the contact interface of adhesive layer and substrate may remarkedly facilitate the adhesion (28). The substrate such as cotton fiber has a zeta potential of −52 mV (29). Therefore, with the increase in the mole percentage of ATC units, i.e., the increase in the number of ATC units as well as the decrease in the number of AA units, it could be imagined that the density of positive charges of S-g-P(ATC-co-AA) layers increased, which gradually enhanced the potential of S-g-P(ATC-co-AA) and generated a substantial effect on the adhesion. Consequently, varying the mole percentage of ATC units on the grafted P(ATC-co-AA) branches is an effective method to strengthen the adhesion of S-g-P(ATC-co-AA) to cotton fibers.

Table 2

Effect of the mole percentage on the zeta potential of S-g-P(ATC-co-AA)

Starches Grafting ratio (%) Mole percentage of ATC units determined on grafted branches (%) Zeta potential (mV)
ACS 0.00 0.00 –1.20
S-g-P(ATC-co-AA) 7.22 19.0 –14.8
7.08 38.1 –1.60
6.96 57.7 +3.90
6.86 77.9 +18.2

Native starch consists of two carbohydrate polymers: linear amylose and branch amylopectin (30). The research points out that the starch paste is a suspension in which the swelled and broken starch particle fragments are dispersed in the continuous phase (31), wherein the continuous phase is a solution of the dissolved amyloses, and the fragments are mainly comprised of branch amylopectin (32). These amylose chains easily arrange in parallel with each other through association between hydroxyl groups, thus forming macromolecular aggregates. Macromolecular aggregates and granule fragments make the paste micro-heterogeneous, unavoidably affecting the wetting and spreading ability of the paste on the fiber surfaces (26). The incomplete wetting and outspreading can induce some damage to adhesion (33) due to the generation of interfacial failure around outspread areas. Additionally, during the conversion of starch paste into starch adhesive layers, the starch paste will shrink in volume with the loss of water. Due to the inherent brittle behavior of starch, the shrinkage will produce high internal stresses at the layer–fiber interfaces and within the layer matrices (26), which are also deleterious to the adhesion (34). Obviously, the grafted P(ATC-co-AA) branches incorporated can exhibit strong steric hindrance. The hindrance can display obvious disturbances to the association of starch hydroxyls and regular arrangement of the amyloses (21), thereby diminishing the paste micro-heterogeneous state. Therefore, the promoted wetting and spreading may be expected to facilitate the adhesion. Moreover, the P(ATC-co-AA) branches can exert an internal plasticization to starch adhesive layers for reducing its internal stresses through their hindrance, thereby promoting the adhesion. Accordingly, based on these positive factors, the adhesion of starch to cotton fibers was improved. Under the similar grafting ratio, as the mole percentage of ATC units raised, a gradually increased bonding forces to cotton fibers for S-g-P(ATC-co-AA) is mainly attributed to the increase in the zeta potential.

3.3 Influence on film properties

Under the similar grafting ratio, the influence of the mole percentage of ATC units on the tensile property (tensile strength and breaking elongation) of starch film was investigated, as depicted in Figure 4. It could be found that the S-g-P(ATC-co-AA) film possessed higher breaking elongation (Figure 4b) but lower tensile strength (Figure 4a) than ACS film, indicating that the incorporation of the P(ATC-co-AA) branches could increase the elongation of starch film but reduce its strength, thus lessening the brittleness of starch film and strengthening its extensibility. As the mole percentage increased from 19.0% to 77.9%, the elongation and strength of S-g-P(ATC-co-AA) film had no obvious variation, which implied that the mole percentage of ATC units did not show significant influences on the film elongation and strength. Undoubtedly, S-g-P(ATC-co-AA) with an extendable film (higher elongation) exhibits an obvious superiority to the ACS for cotton warp sizing.

Figure 4 Influence of the mole percentage of ATC units on the tensile strength (a) and breaking elongation (b) of starch film.
Figure 4

Influence of the mole percentage of ATC units on the tensile strength (a) and breaking elongation (b) of starch film.

During the formation of starch film, the amyloses can form double-stranded helices with each other by the association (35), as well as a double helix with side-branches of amylopectin through the co-crystallization (36). Correspondingly, it will easily lead to the occurrences of regular arrangements, eventually forming three-dimensional regular arrays. This can be described as a major reason that the starch film possesses an inherent brittleness without high deformation. By the steric hindrance, the P(ATC-co-AA) branches can act as wedges to interfere with the association and parallel arrangement during the film-forming process. As a result, a lessened degree of crystallinity can be expected. As shown in Figure 5, the area of crystalline region obtained from the X-ray diffractogram of S-g-P(ATC-co-AA) film (curve a) was obviously lower than that of ACS one (curve b). The degrees of crystallinity of S-g-P(ATC-co-AA) and ACS films were 12.5% and 17.9%, respectively. These revealed that incorporating the P(ATC-co-AA) branches onto the ACS molecules significantly reduced its film crystallinity. The grafted branches diminish the association and parallel arrangement, lower the formation of crystalline structures, consequently exerting an internal plasticization on the starch film and increasing its elongation. In addition, the diminished association and parallel arrangement inevitably lessen the film strength.

Figure 5 X-ray diffractograms of the ACS (a) and S-g-P(ATC-co-AA) (b) films at grafting ratio = 6.96%.
Figure 5

X-ray diffractograms of the ACS (a) and S-g-P(ATC-co-AA) (b) films at grafting ratio = 6.96%.

Besides, the P(ATC-co-AA) branches grafted onto starch molecules can absorb the water in air due to their hydrophilicity. Moisture regain of the S-g-P(ATC-co-AA) film was determined, as presented in Figure 6. As found, the moisture regain of the S-g-P(ATC-co-AA) film was higher than ACS one, which revealed that the hydrophilic branches could raise the regain via absorbing the water in air. Under the similar grafting ratio, the incorporation of the P(ATC-co-AA) branches did not display an obvious influence on the regain of starch film. Water has been considered as an effective plasticizer of starch film (37). Therefore, an increased moisture regain obtained after grafting P(ATC-co-AA) branches onto the starch chains imparts a strong plasticization to the starch film for enhancing its elongation and reducing its strength.

Figure 6 Influence of the mole percentage of ATC units on the moisture regain of starch film.
Figure 6

Influence of the mole percentage of ATC units on the moisture regain of starch film.

Based on the film properties, we concluded that incorporating hydrophilic P(ATC-co-AA) branches onto the starch molecules could reduce the brittleness of starch film and increase its extensibility. However, the mole percentage of ATC units did not display an obvious effect on the film properties of S-g-P(ATC-co-AA) under similar grafting ratio.

3.4 Influence on desizability

It is well known that the use of starch as a sizing agent in warp sizing is temporary, which must be desized from the warps before dyeing, printing, and finishing processes (38). This is because incomplete desizing of starch can lead to a fabric containing a hard handle and poor appearance (26). Accordingly, the starch applied in the warp sizing must possess the property of easy desizing. As is well known, the positively charged starch can produce electrostatic attraction with negatively charged fibers, thereby generating an adverse effect on the desizing of starch from sized warps. Therefore, the effect of the mole percentage of the positively charged ATC units on the P(ATC-co-AA) branches upon the desizing of starch from sized warps must be estimated. Nowadays, desizing efficiency, a mass percentage of sizing agent that desized from sized warps to total sizing agent on sized warps, is commonly adopted to assess the desizability of a sizing agent.

The desizing efficiencies of S-g-P(ATC-co-AA) and control ACS are tabulated in Table 3. As seen in Table 3, the desizing efficiency of S-g-P(ATC-co-AA) gradually reduced from 94.1% to 85.6% as the mole percentage of ATC units increased from 19.0% to 77.9%, which revealed that the incorporation of the positively charged ATC units played an adverse effect on the desizability, and the adverse effect constituted a restriction to the number of ATC units introduced on the P(ATC-co-AA) branches. When the mole percentage was 57.5%, the efficiency (90.5%) was over 90%. However, as the percentage was 77.9%, the efficiency (85.6%) was lower than 90%. Based on the modern textile technology, residual mass percentage of the starch on warps after desizing is commonly required no more than 1 wt% (39), which corresponds to a ≥90% desizing efficiency. The residual starch can be dislodged during the subsequent scouring for smoothly performing the dyeing, printing, and finishing processes. Consequently, the suitable mole percentage of ATC units was approximately 57.7% to avoid the issue of incomplete desizing.

Table 3

Effect of the mole percentage on the desizing efficiency of starch samples

Starches Grafting ratio (%) Mole percentage of ATC units determined on grafted branches (%) Starch add-on (%) Desizing efficiency (%)
ACS 0.00 0.00 9.36 95.3
S-g-P(ATC-co-AA) 7.22 19.0 9.08 94.1
7.08 38.1 9.34 92.4
6.96 57.7 9.51 90.5
6.86 77.9 9.24 85.6

4 Conclusion

The results obtained in this study concluded that the incorporation of the P(ATC-co-AA) branches grafted onto the starch molecules was an effective manner to promote the adhesion of starch to cotton fibers, reduce the brittleness of starch film, and impart the starch with easy desizing for substantially strengthening the end-use ability of starch in warp sizing. Compared with ACS, the S-g-P(ATC-co-AA) possessed the advantages of stronger adhesion, lower film brittleness and easy removal, on the basis of the adhesion, film properties, and desizability. Under the similar grafting ratio, the adhesion to cotton fibers and desizability of S-g-P(ATC-co-AA) were related to the mole percentage of positively charged ATC units incorporated on the P(ATC-co-AA). Increasing the percentage favored the adhesion, but disfavored the desizability and did not display an obvious effect on the film properties of S-g-P(ATC-co-AA). Additionally, the tensile strength, breaking elongation, and moisture regain of S-g-P(ATC-co-AA) film were observed to be insensitive to the mole percentage of grafted P(ATC-co-AA) branches, indicating that increasing the mole percentage of ATC units did not display an obvious effect on the film properties of S-g-P(ATC-co-AA). XRD analysis denoted that the P(ATC-co-AA) branches could lessen the degree of crystallinity of starch film. The desizing trial revealed that the S-g-P(ATC-co-AA) was easily desized from sized cotton warps when the mole percentage of ATC units on the P(ATC-co-AA) branches was ≤57.7%. Considering the results of S-g-P(ATC-co-AA) in the adhesion and film properties, particularly the desizing efficiency, the S-g-P(ATC-co-AA) with a mole percentage of about 57.7% for the ATC units on the P(ATC-co-AA) branches and a grafting ratio of about 7.00% exhibited potential application in the cotton warp sizing.

  1. Funding information: This work was financially supported by the Key Research and Development Project of Anhui Province (No. 201904a06020001), Natural Science Foundation of Anhui Province (No. 1908085ME124), University Youth Talent Support Program of Anhui Province (No. gxyq2022024), and Research Project of Anhui Polytechnic University (No. Xjky2022081), China.

  2. Author contributions: Chaohui Zhang: conceptualization, methodology, writing – original draft, project administration, and funding acquisition; Wei Li: writing – review and editing, funding acquisition, and supervision; Zhenzhen Xu: writing – review and editing, and supervision. The authors applied the SDC approach for the sequence of authors.

  3. Conflict of interest: Authors state no conflict of interest.

  4. Data availability statement: The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

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Received: 2022-12-06
Revised: 2023-01-08
Accepted: 2023-01-12
Published Online: 2023-02-24

© 2023 the author(s), published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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https://doi.org/10.1515/epoly-2022-8109
Keywords for this article
cornstarch; graft polymerization; adhesion; film properties; desizability
Creative Commons
BY 4.0

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  77. Recyclable polytriazole resins with high performance based on Diels-Alder dynamic covalent crosslinking
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  82. Wood-derived high-performance cellulose structural materials
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  84. Polymer-based nanocarriers for biomedical and environmental applications
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  86. Rapid Communication
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  88. Special Issue: Biodegradable and bio-based polymers: Green approaches (Guest Editors: Kumaran Subramanian, A. Wilson Santhosh Kumar, and Venkatajothi Ramarao)
  89. Synthesis and characterization of proton-conducting membranes based on bacterial cellulose and human nail keratin
  90. Fatigue behaviour of Kevlar/carbon/basalt fibre-reinforced SiC nanofiller particulate hybrid epoxy composite
  91. Effect of citric acid on thermal, phase morphological, and mechanical properties of poly(l-lactide)-b-poly(ethylene glycol)-b-poly(l-lactide)/thermoplastic starch blends
  92. Dose-dependent cytotoxicity against lung cancer cells via green synthesized ZnFe2O4/cellulose nanocomposites
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