纺织学报 ›› 2025, Vol. 46 ›› Issue (11): 164-169.doi: 10.13475/j.fzxb.20250303901

• 染整工程 • 上一篇    下一篇

阳离子-丙烯酸酯型接枝淀粉浆料的黏附性能

张朝辉(), 邹梨花, 李伟, 张自豪, 邢晓雨   

  1. 安徽工程大学 纺织服装学院, 安徽 芜湖 241000
  • 收稿日期:2025-03-20 修回日期:2025-08-11 出版日期:2025-11-15 发布日期:2025-11-15
  • 作者简介:张朝辉(1971—),男,正高级实验师,硕士。主要研究方向为纺织浆料的研究与开发。E-mail:autszhangchaohui@163.com
  • 基金资助:
    国家级大学生创新训练计划项目(202310363050)

Adhesion properties of cationic-acrylate grafted starch sizing agent

ZHANG Chaohui(), ZOU Lihua, LI Wei, ZHANG Zihao, XING Xiaoyu   

  1. School of Textile and Garment, Anhui Polytechnic University, Wuhu, Anhui 241000, China
  • Received:2025-03-20 Revised:2025-08-11 Published:2025-11-15 Online:2025-11-15

摘要:

为提高淀粉浆料的黏附性能,以3-丙烯酰胺丙基三甲基氯化铵(ATC)和丙烯酸甲酯(MA)为单体,酸解淀粉(ATS)为原料,在单体总质量为酸解淀粉15%的条件下,通过调整ATC与MA的量比,制备了4种支链中ATC单元摩尔分数不同的接枝淀粉S-g-P(ATC/MA)和S-g-PMA,并对S-g-P(ATC/MA)的分子结构进行表征。分析S-g-P(ATC/MA)的接枝率,研究其黏附性能、浆液Zeta电位及水分散性。结果表明:当单体总量一定时,所制备的S-g-P(ATC/MA)接枝率基本一致;随着支链中ATC单元摩尔分数的增大,其浆液Zeta电位逐渐增大,水分散性逐步改善,对棉纤维、涤纶纤维的黏附力均呈现递增趋势;当支链中ATC单元的摩尔分数由20.5%增至81.1%时,其对棉纤维的黏附力从71.57 N升至76.92 N,对涤纶纤维的黏附力从118.35 N升至127.42 N;此外,S-g-P(ATC/MA)对棉纤维、涤纶纤维的黏附力比S-g-PMA大,S-g-P(ATC/MA)对棉纤维、涤纶纤维的黏附性能优于S-g-PMA。

关键词: 阳离子, 丙烯酸酯, 接枝淀粉, 浆料, 黏附性能, 接枝率

Abstract:

Objective The large number of hydroxyls in starch molecules and the rigid cyclic structure of starch molecules result in insufficient adhesion to fibers, especially polyester and other synthetic fibers, and it is difficult to meet the requirements of warp sizing well. The aim of this study was to prepare a new type of starch-g-poly(3-acrylamidopropyl trimethylammonium chloride/methyl acrylate) [S-g-P(ATC/MA)] used as sizing agent with excellent adhesion properties by introducing both quaternary ammonium cations and ester groups simultaneously into starch molecules through a graft copolymerization reaction, so as to improve the sizing quality.
Method With 3-acrylamidopropyl trimethylammonium chloride (ATC) and methyl acrylate (MA) as monomers and acid-thinned starch (ATS) as raw material, four types of S-g-P(ATC/MA) with different mole fractions of ATC units in the branches were prepared by adjusting the mole ratio of ATC to MA when the total mass of the monomers was 15% of that of ATS. The molecular structures of ATS and S-g-P(ATC/MA) were characterized using an IRPrestige-21 Fourier transformation infrared spectrometer. The nitrogen element and ester group content of S-g-P(ATC/MA) samples were tested by Kjeldahl method and a saponification reaction, respectively, and their grafting ratios were analyzed. The adhesion force of S-g-P(ATC/MA) was obtained by stretching the slightly sized roving using a universal materials testing machine. The Zeta potential and light transmittance of S-g-P (ATC/MA) paste were measured using a Zetasizer Nano-ZS90 analyzer and a UV9600 spectrophotometer, respectively.
Results Comparing the FT-IR spectra of S-g-P(ATC/MA) and ATS, three new sharp absorption peaks appeared in the spectra of S-g-P (ATC/MA). The sharp absorption peak of S-g-P(ATC/MA) at 1 641 cm-1 was attributed to the C=O double bond stretching vibration of amide carbonyl, and the sharp absorption peak at 1 481 cm-1 was attributed to the stretching vibration of C—N. The sharp absorption peaks at these two locations confirmed that the grafted branches contained quaternary ammonium cations. In addition, the sharp absorption peak of S-g-P (ATC/MA) at 1 736 cm-1 was attributed to the stretching vibration of ester carbonyl group. The sharp absorption peak here confirmed that the grafted branches contained ester groups. It was confirmed by FT-IR analysis that S-g-P(ATC/MA) was successfully prepared. When the total amount of monomers is constant, the influence of the mole ratio of ATC to MA on the grafting ratio is not obvious, and the grafting ratio of S-g-P(ATC/MA) prepared is basically the same, all about 7%. When the total amount of monomers is constant, with the increase of the mole fraction of ATC units in the branches, the Zeta potential and light transmittance of S-g-P (ATC/MA) paste increase gradually, and the water dispersibility of S-g-P(ATC/MA) paste gradually improves. When the total amount of monomers is constant, the adhesion force of S-g-P(ATC/MA) to cotton fibers and polyester fibers gradually increases with the increase of the mole fraction of ATC units in the branches. When the mole fraction of ATC units in the branches increases from 20.5% to 81.1%, the adhesion force of S-g-P(ATC/MA) to cotton fibers increases from 71.57 N to 76.92 N, and its adhesion force to polyester fibers increases from 118.35 N to 127.42 N.
Conclusion S-g-P(ATC/MA) increases the Zeta potential of its paste, improves the water dispersibility of its paste, reduces the internal stress and stress concentration within the starch adhensive layer and at the bonding interface by virtue of the hydrophilic quaternary ammonium cations contained in the grafted branches, and thus enhances the adhesion force to fibers. S-g-P(ATC/MA) can improve the adhesion properties to cotton fibers and polyester fibers more compared to S-g-PMA. The successful development of S-g-P(ATC/MA) used as sizing agent will promote the high-value application of starch.

Key words: cation, acrylate, grafted starch, sizing agent, adhesion property, grafting ratio

中图分类号: 

  • TS103.8

图1

ATS和S-g-P(ATC/MA)的红外光谱图"

表1

S-g-P(ATC/MA)和S-g-PMA的接枝率"

淀粉种类 ATC与MA
的量比
支链中ATC单元的
摩尔分数/%
接枝率/
%
S-g-PMA 0∶100 7.09
S-g-P(ATC/MA) 20∶80 20.5 7.11
40∶60 41.1 7.17
60∶40 61.4 7.25
80∶20 81.1 7.32

表2

ATS、S-g-P(ATC/MA)和S-g-PMA的黏附性能"

淀粉种类 支链中ATC单元的
摩尔分数/%
对棉纤维黏附力 对涤纶纤维黏附力
平均值/N CV值/% 平均值/N CV值/%
ATS 58.89 5.36 102.58 6.23
S-g-PMA 69.32 4.85 114.47 6.61
S-g-P(ATC/MA) 20.5 71.57 3.86 118.35 5.79
41.1 73.69 4.22 122.04 6.42
61.4 75.67 4.47 125.43 6.58
81.1 76.92 4.59 127.42 5.35

图2

支链中ATC单元的摩尔分数对浆液Zeta电位的影响"

图3

支链中ATC单元的摩尔分数对浆液透光率的影响"

[1] 彭博, 吴宇洁, 张悦, 等. 低取代度淀粉烷基羧酸单酯的烷基链长对涤纶上浆性能的影响[J]. 纺织学报, 2024, 45(10): 122-127.
PENG Bo, WU Yujie, ZHANG Yue, et al. Influence of alkyl chain length of starch alkyl carboxylic acid monoester with low substitution degree on sizing property of polyester warp yarns[J]. Journal of Textile Research, 2024, 45(10): 122-127.
[2] ZHANG C H, LI W, XU Z Z. Influence of sulfododecenylsuccinylation on the adhesion to fibers and film properties of corn starch for warp sizing[J]. Polymers, 2023, 15(6): 1495.
[3] 李伟, 张正桥, 徐珍珍, 等. 双亲两嵌段接枝淀粉浆料的制备及其上浆性能[J]. 纺织学报, 2022, 43(1): 141-146.
LI Wei, ZHANG Zhengqiao, XU Zhenzhen, et al. Preparation and sizing properties of amphiphilic diblock grafted starch sizing agent[J]. Journal of Textile Research, 2022, 43(1): 141-146.
[4] ZHU Z F, ZHU Z Q. Adhesion of starch-g-poly(2-acryloyloxyethyl trimethyl ammonium chloride) to cotton and polyester fibers[J]. Starch-Stärke, 2014, 66(5/6): 566-575.
[5] 张朝辉, 徐珍珍, 李伟. 季铵阳离子醚化-十二烯基琥珀酸酯化淀粉浆料的黏附性能[J]. 纺织学报, 2018, 39(12): 67-71, 77.
ZHANG Chaohui, XU Zhenzhen, LI Wei. Adhesion properties of quaternary ammonium cation-esterified dodecenylsuccinic anhydride-etherified starch size[J]. Journal of Textile Research, 2018, 39(12): 67-71, 77.
[6] 张朝辉, 徐珍珍, 李伟. 季铵阳离子型接枝淀粉的制备及对纤维的粘合性能[J]. 高分子材料科学与工程, 2018, 34(9): 171-175.
ZHANG Chaohui, XU Zhenzhen, LI Wei. Preparation and adhesion property to fibers of starch-grafted quaternary ammonium cation[J]. Polymer Materials Science & Engineering, 2018, 34(9): 171-175.
[7] 吴兰娟, 祝志峰, 李伟. 两亲性接枝淀粉/PVA混合物的上浆性能研究[J]. 武汉纺织大学学报, 2021, 34(6): 14-19.
WU Lanjuan, ZHU Zhifeng, LI Wei. Study on the properties of PAA-g-S-g-PMA and PVA blend films[J]. Journal of Wuhan Textile University, 2021, 34(6): 14-19.
[8] 张悦, 李伟, 吴宇洁, 等. 丙酸酯化-叔胺化淀粉浆料的制备及其黏附性能[J]. 纺织学报, 2024, 45(1): 146-151.
ZHANG Yue, LI Wei, WU Yujie, et al. Preparation and adhesion properties of propionylated-tertiary aminated starch sizing agent[J]. Journal of Textile Research, 2024, 45(1): 146-151.
[9] XU Z Z, ZHU Z F, LI W, et al. Amphiphilic starch with 3-(trimethylammonium chloride)-2-hydroxypropyl and octenylsuccinyl substituents for strong adhesion to fibers[J]. Journal of Adhesion Science and Technology, 2018, 32(6): 609-624.
[10] LI T, XIANG S F, MA P M, et al. Nanocomposite hydrogel consisting of Na-montmorillonite with enhanced mechanical properties[J]. Journal of Polymer Science Part B: Polymer Physics, 2015, 53(14): 1020-1026.
[11] WANG Y B, XIE W L. Synthesis of cationic starch with a high degree of substitution in an ionic liquid[J]. Carbohydrate Polymers, 2010, 80(4): 1172-1177.
[12] ALTUNA L, HERRERA M L, FORESTI M L. Synthesis and characterization of octenyl succinic anhydride modified starches for food applications: a review of recent literature[J]. Food Hydrocolloids, 2018, 80: 97-110.
[13] JACOBASCH H J, BAUBÖCK G, SCHURZ J. Problems and results of zeta-potential measurements on fibers[J]. Colloid and Polymer Science, 1985, 263(1): 3-24.
[14] ZHU Z F, LEI Y. Effect of chain length of the alkyl in quaternary ammonium substituents on the adhesion-to-fiber, aerobic biodegradation, and desizability of quaternized cornstarch[J]. Journal of Adhesion Science and Technology, 2015, 29(2): 116-132.
[15] 祝志峰. 纺织工程化学[M]. 上海: 东华大学出版社, 2010: 179-217.
ZHU Zhifeng. Chemistry in textile engineering[M]. Shanghai: Donghua University Press, 2010: 179-217.
[16] 李伟. 马来酸酯系淀粉衍生物的制备和低温上浆性能研究[D]. 无锡: 江南大学, 2015:53-56.
LI Wei. Preparation and low-temperature sizing properties of maleate starch derivatives[D]. Wuxi: Jiangnan University, 2015:53-56.
[1] 陈晴宇, 陆春红, 张斌, 晋义凯, 黄琪帏, 王超, 丁彬, 俞建勇, 王先锋. 碳纤维增强水泥基灌浆料的制备及其性能[J]. 纺织学报, 2025, 46(08): 120-126.
[2] 刘宇祥, 乌婧, 徐锦龙, 谢锐敏, 王华平. 阳离子可染聚对苯二甲酸丙二醇酯预取向丝的制备及其性能[J]. 纺织学报, 2025, 46(07): 46-52.
[3] 林玉婷, 许仕林, 胡毅. 多色彩热塑性聚氨酯/聚丙烯腈纳米纤维纱线的制备及其性能[J]. 纺织学报, 2025, 46(07): 78-86.
[4] 赵强强, 王韩星, 张奉轩, 何瑾馨, 周俊, 周兆昌, 董霞. 聚六亚甲基双胍盐酸盐改性对棉织物耐日晒色牢度的影响[J]. 纺织学报, 2025, 46(04): 109-118.
[5] 彭博, 吴宇洁, 张悦, 李妙龙, 孟祥, 李伟, 鲁育豪. 低取代度淀粉烷基羧酸单酯的烷基链长对涤纶上浆性能的影响[J]. 纺织学报, 2024, 45(10): 122-127.
[6] 韩画宇, 杨文龙, 王甫, 胡柳, 胡毅. 苯并[a]吩恶嗪基功能染料制备及其在改性涤纶织物上的应用[J]. 纺织学报, 2024, 45(10): 128-136.
[7] 郑康, 龚文丽, 鲍杰, 刘琳. 两性纤维素多孔凝胶球的制备及其动态吸附性能[J]. 纺织学报, 2024, 45(05): 102-112.
[8] 张悦, 李伟, 吴宇洁, 程雪冬, 孟祥. 丙酸酯化-叔胺化淀粉浆料的制备及其黏附性能[J]. 纺织学报, 2024, 45(01): 146-151.
[9] 杜姗, 魏云航, 谭宇浩, 吴婷, 李勇, 杨红英, 王明, 周伟涛. 棉织物的硅溶胶/短链含氟聚丙烯酸酯复合拒水整理[J]. 纺织学报, 2023, 44(09): 153-160.
[10] 葛佳慧, 毛志平, 张琳萍, 钟毅, 隋晓锋, 徐红. 基于二维碳化钛材料修饰的功能棉针织物制备及其性能[J]. 纺织学报, 2023, 44(04): 132-138.
[11] 孙将皓, 邵彦峥, 魏春艳, 王迎. 海藻酸钠/改性氧化石墨烯微孔气凝胶纤维制备与吸附性能[J]. 纺织学报, 2023, 44(04): 24-31.
[12] 肖明, 黄亮, 罗龙永, 毕曙光, 冉建华. 羧基化聚苯乙烯荧光微球的合成及其在织物防伪中的应用[J]. 纺织学报, 2023, 44(02): 184-190.
[13] 张楚丹, 王锐, 王文庆, 刘燕燕, 陈睿. 阳离子改性阻燃涤纶织物的制备及其性能[J]. 纺织学报, 2022, 43(12): 109-117.
[14] 王瑞, 司银松, 芦浩浩, 杲爽, 傅雅琴. 基于近红外光谱法的桑蚕丝接枝率快速定量测定[J]. 纺织学报, 2022, 43(11): 29-34.
[15] 谢子文, 李家炜, 汪芬萍, 戚栋明, 严小飞, 朱晨凯, 赵磊, 何贵平. 有机硅改性水性聚氨酯丙烯酸酯杂化胶乳的制备及其在涂料印花中的应用[J]. 纺织学报, 2022, 43(08): 119-125.
Viewed
Full text


Abstract

Cited

  Shared   
  Discussed   
No Suggested Reading articles found!