Fibers nd Polymers 2017, Vol.18, No.11, 2255-2260 DOI 10.1007/s12221-017-1027-7 Communiction ISSN 1229-9197 (print version) ISSN 1875-0052 (electronic version) Effect of Glss Trnsition Tempertures nd Zet Potentils of Ctionic Copolymer Ltexes on Pigment Dyeing Kunjun Fng 1,2,3 *, Hining Go 2, Fuyun Sun 2, Weicho Chen 2, Ruyi Xie 2, nd Yuqing Ci 2 1 Lbortory of Fiber Mterils nd Modern Textiles, The Growing Bse for Stte Key Lbortory, Shndong 266071, People s Republic of Chin 2 College of Textile nd Apprel, Qingdo University, Shndong 266071, People s Republic of Chin 3 Collbortive Innovtion Center for Eco-textiles of Shndong Province, Shndong 266071, People s Republic of Chin (Received October 28, 2016; Revised August 17, 2017; Accepted August 19, 2017) Abstrct: Cotton fbrics treted by ctionic copolymers show better wet rubbing fstness nd hndle thn the conventionl nion binders. However, the effect of glss trnsition tempertures nd zet potentils of ctionic copolymer ltex on pigment dyeing hs not been reported. In the present study, three different kinds of p(st-co-ba) ctionic ltexes were synthesized by emulsion copolymeriztion. The prepred ctionic copolymer ltexes were ll uniform sphericl prticles s shown by the TEM imges. The glss trnsition tempertures nd zet potentils of the three kinds of ltexes were -3.3 o C nd 58.5 mv for St:BA=7:13, 13.4 o C nd 65.9 mv for St:BA=9:11, 18.1 o C nd 61.3 mv for St:BA=11:9. Cotton fbrics treted with 2.0 % ctionic ltexes produced idel pigment dyeing performnce. Compring the color results, the ltex (St:BA=9:11) hd the highest color depth, the ltex (St:BA=11:9) took the second plce, while the ltex (St:BA=7:13) gve the lightest color. The pigment dyeing performnce of the ltex is closely relted to the zet potentil nd the glss trnsition temperture. Keywords: Ctionic copolymer ltexes, Glss trnsition tempertures, Zet potentils, Cotton fbrics, Pigment dyeing Introduction Pigment dyeing of textiles hs mny dvntges, such s simple nd short product process, little wstewter nd low production cost [1]. However, pigments re insoluble nd hve no ffinity to fibers. Therefore, binders re required to fix pigment prticles on the fiber surfce to give colorfstness [1-3]. The performnce of the binder gretly ffects the qulity of the dyed fbric nd plys n importnt role in pigment dyeing of textiles [1,4]. The binders used for pigment dyeing re mostly negtively chrged nd hve the sme chrge s the cotton fibers nd the pigment prticles. Thence, they re more suitble for light color dyeing. Besides, conventionl pigment dyeing hs the drwbcks in terms of wet rubbing fstness nd corse hndle [1,5,6]. Therefore, ctionic binders hve ttrcted lot of ttentions becuse they hve sttic ttrctive forces to fibers [5]. A ctionic binders synthesized by emulsion copolymeriztion showed better stbility, wet rubbing fstness nd hnd feeling thn the conventionl nion binders [5,7]. Styrene-crylic ctionic emulsions with high solid content prepred by emulsifier-free emulsion copolymeriztion hd the dvntges of good wter-resistnce nd fvorble stbility [7]. The poly(styrene-co-crylic cid)(st/aa) colloids exhibited enhnced colloid stbility nd surfce chrge density [5]. The glss trnsition tempertures of the binder polymers ply n importnt role in the fixtion of the pigment prticles on the fiber surfce [7,8]. The objective of the present work *Corresponding uthor: 13808980221@163.com ws focused on the effect of glss trnsition tempertures of ctionic copolymers on pigment dyeing. Three ctionic ltexes with different rtios of styrene (St) nd butyl crylte (BA) were synthesized by emulsion copolymeriztion. We lso investigted the colloidl chrcteristics nd their effect on pigment dyeing, such s the instntneous conversion, prticle size, prticle number nd color performnce. Experimentl Mterils Styrene (A.R.), purchsed from Tinjin Gungcheng Chemicl Regent Co., Ltd. (Tinjin, Chin), ws firstly wshed three times with 10 wt% sodium hydroxide queous solution to remove the inhibitor, then wshed three times with deionized wter nd stored t -18 o C for usge. Butyl crylte (A.R.) ws purchsed from Tinjin Dmo Chemicl Regent Co., Ltd. (Tinjin, Chin). 2,2'-Azobis (N,N'- dimethyleneisobutyrmidine) dihydrochloride (purity >98 %) ws provided by Qingdo Kexin New Mteril Co. (Qingdo, Chin). Hexdecyl trimethyl mmonium chloride ws purchsed from Shnghi Aibi Chemistry Preprtion Co. (Shnghi, Chin). Ctionic Emulsion Copolymeriztion of St nd BA The copolymeriztion ws crried out in 250 ml roundbottomed flsk equipped with stinless steel stirrer, nitrogen inlet tube, nd reflux condenser. Firstly, the nitrogen ws injected into the flsk nd then certin mount of deionized wter ws dded. The emulsifier ws dded into the queous solution nd stirred t 250 rpm for 30 min to mke the 2255
2256 Fibers nd Polymers 2017, Vol.18, No.11 Kunjun Fng et l. Tble 1. The mounts of emulsifier, copolymeriztion inititor nd monomers used in the ctionic emulsion copolymeriztion St (g) BA (g) CTAC (g) AIBA (g) 7.0 13.0 1.2 0.1 9.0 11.0 1.2 0.1 11.0 9.0 1.2 0.1 The rection temperture, 80 o C; the stirring speed, 300 r/min; the rection time, 4 h. uniform dispersion. The rection system ws heted to 80 o C fter the mixture of St nd BA ws dded. Then certin mount of inititor ws dded, nd the rection system ws kept t 80 o C for 3 h until the end of the rection. The mount of emulsifier, copolymeriztion inititor nd monomers used in the ctionic emulsion copolymeriztion were shown in Tble 1. Monomer Conversion Determintion The monomer conversion ws determined grvimetriclly. After the rection, smple ws plced in clen nd dry weighed bottle. A drop of hydroquinone solution with mss frction of 0.5 % ws dded into the bottle, then dried t 100 o C for 2 h to constnt weight. The conversion rte (C) is clculted s follows [9,10]: m C 1 /m = ------------------------------ 2 m c /( m c + m w ) 100% where, m 1 is the qulity of the smple fter drying (g); m 2 is the qulity of the smple before drying (g); m c is the qulity of ll monomers (g); m w is the qulity of wter (g). Prticle Sizes, Size Distributions nd Zet Potentils The hydrodynmic verge prticle size, prticle size distribution nd zet potentil were determined using Mlvern Nnozs90 lser prticle size nlyzer. The emulsions were diluted 1,000-fold before determintion. Morphologies of the Ltex Prticles The ltex prticles were ultrsoniclly diluted 25 times with deionized wter nd dropped onto Cu meshes. After drying under n infrred lmp, the size nd morphology of the P (St-co-BA) prticles were observed using JEM-1200 EX trnsmission electron microscope (JEOL, Jpn) [11,12]. Mesurement of Glss Trnsition Tempertures Tg ws mesured using Pyris Dimond differentil scnning clorimeter (Perkins Elmer Instruments Inc of USA). The emulsions were demulsified by NCl nd wshed three times with deionized wter, nd then sesoned t 70 o C [13]. Film Formtion on Cotton Fibers The cotton fbrics were soked in dispersion with 0.5 g/l solid content ltexes under oscillting t 25 o C for 2 h. The soked fbrics were dried t room temperture. The morphology of ltex prticles on the fiber surfces ws observed vi n S-4800 field emission scnning electron microscope (Hitchi, Jpn). Fbric Dyeing nd Color Mesurements The cotton fbrics were wshed 3 times using 80 o C wter. Ech wshing ws kept for 10 min. The wshed fbrics were dried t 60 o C. Then, the fbrics were dipped in ctionic ltex dispersion with bth rtio of 50:1. The tretment bth ws heted to 50 o C nd remined for 60 min under oscillting. The treted fbrics were tken out of the bth nd dyed in pigment dispersion bth t 70 o C for 2 h. The dyed fbrics were dried t 80 o C for 3 min nd bked t 120 o C for 5 min. The color of dyed fbric ws mesured using SP60 integrting sphere spectrophotometer (X-Rite, USA). The reltive color strength of the cotton fbric ws expressed s the K/S vlue [14,15]. Rubbing Fstness Mesurements Rubbing fstness of the dyed cotton fbrics ws tested ccording to ISO 105-X12 stndrd. Results nd Discussion Colloidl Fetures of the Ltex Tble 2 shows the monomer conversions nd solid contents of prepred emulsions. It cn be seen tht the monomer conversion incresed from 94.4 % to 99.2 % with chnging the rtio of St:BA from 7:13 to 11:9 while the solid content remined unchnged [14,16]. As shown in Figure 1, the prticle size distribution of ltex vried with the monomer rtio. The widest size distribution ws obtined t St:BA rtio of 7:13, nd the nrrowest t 11:9. However, the verge prticle size ws the sme, 49.2 nm, for the 7:13 nd 11:9 smples, while the verge prticle size of the 9:11 smple ws 46.4 nm, smller thn 49.2 nm, s shown Tble 3. The ltex of St:BA=9:11 hd the highest zet potentil, 65.9 mv, nd the ltex of St:BA=7:13 hd the lowest zet potentil, 58.5 mv, the ltex of St:BA= 11:9 ws 61.3 mv. These dt indictes tht the prepred ltex prticles hd excellent stbility [17,18]. Tble 3 lso gives the glss trnsition tempertures of different ltexes, the T g of St:BA=7:13, St:BA=9:11 nd Tble 2. Monomer conversions nd solid contents St :BA Solid contents (%) Conversions rtes (%) 7:13 19.8 94.4 9:11 19.9 98.4 11:9 19.9 99.2 The copolymeriztion temperture, 80 o C; the stirring rte, 300 r/ min; the rection time, 4 h.
Ctionic Copolymer Ltexes on Pigment Dyeing Fibers nd Polymers 2017, Vol.18, No.11 2257 St:BA=11:9 were -3.3 o C, 13.4 o C nd 18.1 o C in turn. It is cler tht incresing the rigid monomer, styrene, resulted in the T g increse of the copolymer ltex. Conversely, incresing the soft monomer, butyl crylte, could decrese the T g of the copolymer ltex [14,18]. As shown in Figure 2, the TEM imges indicte tht the three kinds of ltex prticles re ll uniform sphericl prticles [19,20]. Film Formtion of the Ctionic Ltex on the Cotton Fibers Figure 3 is the SEM imges of cotton fibers. It cn be seen tht the originl cotton fiber surfce hd lot of grooves (Figure 3()). The fiber surfce becme smooth fter treted with the copolymer (St:BA=7:13) ltexes (Figure 3(b)), indicting tht the ctionic ltexes formed uniform film on the fiber surfces nd covered the grooves. However, the fiber surfces becme rough fter treted with the copolymer ltexes (St:BA=9:11) (Figure 3(c)). And closely pcked ltex prticles on the fiber surfces (Figure 3(d)) were found fter treted by the copolymer (St:BA=11:9) [21-23]. Figure 1. Size distribution of ltex prticles; () St:BA=7:13, (b) St:BA=9:11, nd (c) St:BA=11:9. Tble 3. Colloidl fetures of the ltex prticles St:BA Averge prticles size (nm) Zet (mv) T g ( o C) 7:13 49.2 58.5-3.3 9:11 46.4 65.9 13.4 11:9 49.2 61.3 18.1 The scnning temperture, -50-150 o C; the heting rte, 10 o C/min. Pigment Dyeing Performnce The influence of temperture nd time on the pigment dyeing were investigted using the copolymer (St:BA=9:11). The results were shown in Figure 4. Incresing the dyeing temperture from 10 o C to 70 o C resulted in incresing the K/S vlues of dyed fbrics (Figure 4()). However, the K/S vlues only slightly improved with further incresing the dyeing temperture to bove 70 o C [24-26]. Figure 4(b) shows tht the K/S vlue of the dyed fbric incresed quickly with prolonging the dyeing time from 30 min to 120 min. However, the K/S vlue incresed slowly bove 120 min. Therefore, the dyeing temperture nd time were selected s 70 o C nd 120 min, respectively, which were lso used for the dyeing of the other two copolymers to fcilitte better comprison [27,28]. As shown in Tble 4, incresing the ltex (St:BA=7:13) mount of from 1.0 % to 2.0 % evidently decresed the L * vlue from 84.9 to 55.4, * vlue rised from 11.7 to 36.7, b * vlue reduced from 5.9 to 4.3, the K/S vlue incresed shrply from 0.2 to 3.4. Further incresing the ltex mount Figure 2. TEM imges of the ctionic copolymer ltexes; () St:BA=7:13, (b) St:BA=9:11, nd (c) St:BA=11:9.
2258 Fibers nd Polymers 2017, Vol.18, No.11 Kunjun Fng et l. Figure 3. SEM imges of the cotton fibers; () the originl cotton fibers, (b) the cotton fibers treted with the copolymer of St:BA= 7:13, (c) the cotton fibers treted with the copolymer of St:BA=9:11, nd (d) the cotton fibers treted with the copolymer of St:BA=11:9. Figure 4. Effect of dyeing tempertures nd time on the pigment dyeing of the copolymer (St:BA=9:11); () the dyeing temperture nd (b) the dyeing time. Tble 4. Pigment dyeing color prmeters nd rubbing fstness of the cotton fbrics treted by the ctionic copolymer (St:BA=7:13) Ltex mount Rubbing fstness L * * b * K/S (%, owf) Dry Wet 1.0 84.9 11.7 5.9 0.2 5 4-5 2.0 55.4 36.7 4.3 3.4 4-5 4 3.0 53.5 36.2 4.4 3.7 4-5 4 4.0 54.3 35.6 3.3 3.4 4-5 4 5.0 53.8 36.2 3.5 3.6 4-5 4 The ltex tretment ws conducted t 50 o C for 60 min. The pigment dyeing ws performed t 50 o C for 2 h using 1 % pigment RED HH-B (owf). The dyed fbric ws dried t 80 o C for 3 min nd bked t 120 o C for 5 min.
Ctionic Copolymer Ltexes on Pigment Dyeing Fibers nd Polymers 2017, Vol.18, No.11 2259 Tble 5. Pigment dyeing color prmeters nd rubbing fstness of the cotton fbrics treted by the ctionic copolymer (St:BA=9:11) Ltex mount Rubbing fstness L (%, owf) * b * K/S Dry Wet 1.0 81.6 19.8 5.8 0.3 5 4-5 2.0 48.2 52.6 8.6 6.3 4 3-4 3.0 48.3 52.5 8.0 6.4 4 3-4 4.0 48.3 53.0 8.3 6.4 4 3-4 5.0 48.1 54.3 8.7 6.9 4 3-4 The ltex tretment ws conducted t 50 o C for 60 min. The pigment dyeing ws performed t 50 o C for 2 h using 1 % pigment RED HH-B (owf). The dyed fbric ws dried t 80 o C for 3 min nd bked t 120 o C for 5 min. Tble 6. Pigment dyeing color prmeters nd rubbing fstness of the cotton fbrics treted by the ctionic copolymer (St:BA=11:9) Ltex mount Rubbing fstness L (%, owf) * b * K/S Dry Wet 1.0 81.8 23.7 10.6 0.4 5 4-5 2.0 57.1 51.7 19.8 5.2 4 3-4 3.0 56.5 53.5 22.1 6.1 4 3-4 4.0 55.3 53.9 22.4 6.8 4 3-4 5.0 55.3 54.1 23.1 6.8 4 3-4 The ltex tretment ws conducted t 50 o C for 60 min. The pigment dyeing ws performed t 50 o C for 2 h using 1 % pigment RED HH-B (owf). The dyed fbric ws dried t 80 o C for 3 min nd bked t 120 o C for 5 min. from 2.0 % to 5.0 %, the color vlues were nerly unchnged due to the sturted dsorption of ltex prticles on the fiber surfces [11,29]. The rubbing fstness decresed fter the ltex mount incresed to 2 % nd bove becuse the more pigments were fixed nd deep colors were obtined [28,30]. The color nd rubbing fstness properties of the fbrics treted by the ctionic ltex (St:BA=9:11) (Tble 5) nd the ltex (St:BA=11:9) (Tble 6) exhibited the sme vrition trend s the ltex (St:BA=7:13). Compring the results of the three kinds of ltex, the ltex (St:BA=9:11) produced the highest color depth, the ltex (St:BA=11:9) took the second plce, while the ltex (St:BA=7:13) gve the lightest color, lmost hlf of the ltex (St:BA=9:11). This result is closely relted to the zet potentil sequence: 65.9 mv (St:BA=9:11) > 61.3 mv (St:BA=11:9) > 58.5 mv (St:BA=7:13) becuse the higher the zet potentil the more positive chrges endowed on the fiber surfces nd the more pigment prticles dsorbed. The color strength of the dyed fbric is lso relted to the glss trnsition tempertures in some extent. Lower ltex T g resulted in more trnsprent nd uniform film formtion on the fiber surfce (Figure 3(b)), which led to lower color strength due to certin loss of the positive chrges. However, higher ltex T g formed uneven film on the fiber surfces through closely pcking of the ltex prticles (Figure 3(c) nd 3(d)), which led to higher color strength due to less loss of the positive chrges. Conclusion Three kinds of ctionic ltex prticles were prepred by chnging the rtio of styrene nd butyl crylte using emulsion copolymeriztion. TEM imges showed tht the ctionic copolymer ltexes were uniform sphericl prticles. The glss trnsition tempertures nd zet potentils of the three kind of ltexes were -3.3 o C nd 58.5 mv for St:BA= 7:13, 13.4 o C nd 65.9 mv for St:BA=9:11, 18.1 o C nd 61.3 mv for St:BA=11:9. Cotton fbrics treted with 2.0 % ctionic ltexes produced idel pigment dyeing performnce. Compring the color results, the ltex (St:BA=9:11) produced the highest color depth, the ltex (St:BA=11:9) took the second plce, while the ltex (St:BA=7:13) gve the lightest color. The pigment dyeing performnce of the ltex is closely relted to the zet potentil nd the glss trnsition temperture. Acknowledgement This work ws finncilly supported by Ntionl Nturl Science Foundtion of Chin, Grnt No. 51173086; Ntionl Key Technology R&D Progrm, Grnt No. 2017YFB0309801, 2017YFB0309803, 2017YFB0309804; Tishn scholrs for construction engineering nd Tishn progrms for scientific reserch innovtion tem in colleges nd universities of Shndong province; Appliction Bsis nd Cutting-edge Technology Reserch Project of Tinjin, Grnt No.: 14JCZDJC37200. References 1. K. J. Fng, C. X. Wng, X. Zhng, nd Y. Xu, Color.
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