纺织学报 ›› 2021, Vol. 42 ›› Issue (01): 10-15.doi: 10.13475/j.fzxb.20200606006

• 纤维材料 • 上一篇    下一篇

溶胶-凝胶法改性阻燃粘胶纤维的制备及其性能

马君志1,2, 葛红2, 王冬1, 付少海1()   

  1. 1.生态纺织教育部重点实验室(江南大学), 江苏 无锡 214122
    2.恒天海龙(潍坊)新材料有限责任公司, 山东 潍坊 261100
  • 收稿日期:2020-06-19 修回日期:2020-10-18 出版日期:2021-01-15 发布日期:2021-01-21
  • 通讯作者: 付少海
  • 作者简介:马君志(1976—),男,博士生。主要研究方向为阻燃再生纤维素纤维。
  • 基金资助:
    国家重点研发计划项目(2017YFB0309004);江苏省自然科学基金项目(BK20190613)

Preparation and properties of sol-gel modified flame retardant viscose fiber

MA Junzhi1,2, GE Hong2, WANG Dong1, FU Shaohai1()   

  1. 1. Key Laboratory of Eco-Textiles (Jiangnan University), Ministry of Education, Wuxi, Jiangsu 214122, China
    2. CHTC Helon (Weifang) New Materials Co., Ltd., Weifang, Shandong 261100, China
  • Received:2020-06-19 Revised:2020-10-18 Online:2021-01-15 Published:2021-01-21
  • Contact: FU Shaohai

摘要:

为提升粘胶/二硫代焦磷酸酯(VF/DDPS)纤维的阻燃性能,通过溶胶-凝胶法,采用正硅酸四乙酯(TEOS)对VF/DDPS纤维表面进行阻燃改性,得到阻燃粘胶纤维(VF/DDPS/TEOS)。借助扫描电子显微镜、X射线光电子能谱仪、热重分析仪、锥形量热仪、微型量热仪、单纤强力仪等对改性纤维的结构和性能进行分析。结果表明:改性后VF/DDPS/TEOS纤维的阻燃性能提高,其在750 ℃时的残炭量从3.23%增加到7.93%,引燃时间从4 s延长至16 s,热释放速率峰值和总热释放量分别下降了19.3%和16.0%,极限氧指数从28.2%升高至29.3%;VF/DDPS/TEOS纤维表面形成了致密的氧化硅保护膜,二氧化硅在纤维燃烧过程中显著增强了纤维表面炭层的热质阻隔作用;阻燃整理后纤维的断裂强度、断裂伸长率及吸湿性能均有所降低。

关键词: 粘胶纤维, 溶胶-凝胶法, 二硫代焦磷酸酯, 正硅酸四乙酯, 阻燃性能

Abstract:

In order to improve the flame-retardant properties of viscose/dithiopyrophosphate (VF/DDPS) fibers, the sol-gel technology was used to modify the VF/DDPS fiber surface via the hydrolysis of tetraethyl orthosilicate (TEOS). The structures and properties of the modified flame retardant viscose fibers (VF/DDPS/TEOS) were characterized by means of scanning electron microscope, X-ray photoelectron spectroscopy, thermogravimetric analyzer, cone calorimeter,micro combustion calorimeter, and single fiber strength analyzer. The results show that the flame retardancy of VF/DDPS/TEOS fiber was improved with the increase of char residues from 3.23% to 7.93% at 750 ℃. Moreover, the ignition time of VF/DDPS/TEOS fiber is extended from 4 s to 16 s, peak heat release rate and total heat release are decreased by 19.3% and 16.0% respectively, and limiting oxygen index is increased from 28.2% to 29.3%. The surface of VF/DDPS/TEOS fibers forms a dense silica protective film, and the silica significantly enhances the thermal and mass barrier of the carbon layer on the fiber surface during combustion. However, the breaking strength, elongation at break and hygroscopicity of the modified fiber are decreased.

Key words: viscose fiber, sol-gel method, bisneopentyl glycol dithiopyrophosphate, tetraethyl orthosilicate, flame retardancy

中图分类号: 

  • TS102.6

图1

TEOS阻燃改性前后纤维SEM照片"

图2

TEOS阻燃改性前后纤维的TG和DTG曲线"

图3

TEOS阻燃改性前后纤维的燃烧性能"

表1

纤维的燃烧性能数据"

样品名称 锥形量热仪 微型量热仪 极限氧
指数值/%
引燃
时间/s
熄火
时间/s
热释放速率峰值/
(kW·m-2)
总放热量/
(MJ·m-2)
热释放速率峰值/
(W·g-1)
燃烧热量/
(J·g-1)
点燃
温度/℃
VF/DDPS 4 198 128.5 11.9 229.4 7.5 285.9 28.2
VF/DDPS/TEOS 16 112 123.1 10.8 185.1 6.3 287.1 29.3

图4

TEOS阻燃改性前后纤维的热释放速率曲线"

图5

TEOS阻燃改性前后纤维炭渣SEM照片(×6 000)"

图6

TEOS阻燃改性前后纤维炭渣XPS谱图"

表2

TEOS阻燃改性前后纤维力学及吸湿性能指标"

样品 干断裂强度/
(cN·dtex-1)
湿断裂强度/
(cN·dtex-1)
干断裂
伸长率/%
回潮率/
%
VF/DDPS 2.18 1.20 20.8 11.60
VF/DDPS/TEOS 2.09 1.06 17.1 10.95
[1] 郭雪花.用于纺织品功能整理的溶胶凝胶技术[J].轻工科技, 2011, 27(6): 27, 33.
GUO Xuehua. Sol-gel technology for textile functional finishing [J]. Guangxi Journal of Light Industry, 2011, 27(6): 27, 33.
[2] SAIF M J, ZIA K M, REHMAN F, et al. An eco-friendly, permanent, and non-leaching antimicrobial coating on cotton fabrics[J]. Journal of The Textile Institute, 2014,106(9):907-911.
[3] COLLEONI C, DONELLI I, FREDDI G, et al. A novel sol-gel multi-layer approach for cotton fabric finishing by tetraethoxysilane precursor[J]. Surface & Coatings Technology, 2013,235(22):192-203.
[4] ALONGI J, CIOBANU M, TATA J, et al. Thermal stability and flame retardancy of polyester, cotton, and relative blend textile fabrics subjected to sol-gel treatments[J]. Journal of Applied Polymer Science, 2011,119(4):1961-1969.
[5] HRIBERNIK S, SMOLE M S, KLEINSCHEK K S, et al. Flame retardant activity of SiO2-coated regenerated cellulose fibres[J]. Polymer Degradation and Stability, 2007,11(11):1957-1965.
[6] 赵虎. Sol-Gel法制备硅溶胶及对粘胶纤维的改性研究[D]. 广州:华南理工大学, 2015: 34-35.
ZHAO Hu. Study on the preparation of silica sol by Sol-Gel method and the modification of viscose fiber[D]. Guangzhou:South China University of Technology, 2015: 34-35.
[7] ALTLNTAS Z, CAKMAKCL E, KAHRAMAN M V, et al. Preparation of photocurable silica-titania hybridcoatings by an anhydrous sol-gel process[J]. Journal of Sol-Gel Science and Technology, 2011,58(3):612-618.
[8] 邱春阳, 张克铮. 二氧化硅溶胶稳定性的研究[J]. 辽宁石油化工大学学报, 2005,25(2):1-4.
QIU Chunyang, ZHANG Kezheng. The stability of SiO2 sol[J]. Journal of Liaoning University of Petroleum & Chemical Technology, 2005,25(2):1-4.
[9] 刘元美, 高琴文, 朱泉, 等. 纯棉织物耐久阻燃整理工艺[J].纺织科技进展, 2008(5):4-6.
LIU Yuanmei, GAO Qinwen, ZHU Quan, et al. Study on durable flame-retardant finishing of cotton fabrics[J]. Progress in Textile Science & Technology, 2008(5):4-6.
[10] 程明明, 纪全, 夏延致, 等. 阻燃粘胶纤维的热降解性能研究[J]. 合成纤维工业, 2009,32(2):11-13.
CHENG Mingming, JI Quan, XIA Yanzhi, et al. Study on thermal degradation of flame retardant viscose fiber[J]. China Synthetic Fiber Industry, 2009,32(2):11-13.
[11] DENG Yi, WANG Yuzhong, BAN Danling, et al. Burning behavior and pyrolysis products of flame-retardant PET containing sulfur-containing aryl Polyphosphonate[J]. Journal of Analytical and Applied pyrolysis, 2006,76(6):198-202.
[12] 宋翠翠. 过渡金属氧化物对粘胶纤维热稳定性与燃烧性能的影响[D]. 青岛:青岛大学, 2014: 39-41.
SONG Cuicui. Effect of transition metal oxide on thermal stability and combustion performance of viscidity fiber[D]. Qingdao:Qingdao University, 2014: 39-41.
[13] WANNA J T, POWELL J E. Thermal decomposition of cotton cellulose treated with selected salts[J]. Thermochimica Acta, 1993(226):257-263.
[14] 徐婕, 朱宏, 陈国强, 等. 微型量热仪在纺织品燃烧性能测试中的应用[J]. 印染, 2013,39(18):38-40,56.
XU Jie, ZHU Hong, CHEN Guoqiang, et al. Determination of flammability of textiles by micro combustion calorimeter[J]. China Dyeing & Finishing, 2013,39(18):38-40,56.
[15] 周颖雨, 王文庆, 王锐. 层层自组装法制备阻燃织物的研究进展[J]. 北京服装学院学报(自然科学版), 2019,39(4):87-98.
ZHOU Yingyu, WANG Wenqing, WANG Rui. Research progress on the synjournal of flame retardant textiles using layer-by-layer self-assembly technology[J]. Journal of Beijing Institute of Fashion Technology (Natural Science Edition), 2019,39(4):87-98.
[16] 刘力锋, 陈诺夫, 张富强, 等. 低能离子束方法制备Fe组分渐变的Fe-Si薄膜[J].稀有金属, 2004(3):558-562.
LIU Lifeng, CHEN Nuofu, ZHANG Fuqiang, et al. Iron conten gradually variational Fe-Si film prepared by low-energy ion beam method[J]. Rare Metals, 2004(3):558-562.
[17] 周丹, 刘博, 陈思远, 等. 磷掺杂碳材料的制备、表征及应用进展[J]. 工业催化, 2020,28(6):7-11.
ZHOU Dan, LIU Bo, CHEN Siyuan, et al. Progress in preparation, characterization and application of phosphorus-doped carbon materials[J]. Industrial Catalysis, 2020,28(6):7-11.
[18] 邱秀丽, 刘正芹, 于丽华, 等. 功能粘胶纤维的耐酸碱性[J]. 山东纺织科技, 2010,51(6):51-53.
QIU Xiuli, LIU Zhengqin, YU Lihua, et al. Resistance to acid and alkal of functional viscose fibers[J]. Shandong Textile Science and Technology, 2010,51(6):51-53.
[1] 曾凡鑫, 秦宗益, 沈玥莹, 陈园余, 胡铄. 自熄性棉织物的喷涂辅助层层自组装法制备及其阻燃性能[J]. 纺织学报, 2021, 42(01): 103-111.
[2] 刘晋旭, 刘鹏清. 织物阻燃表面处理技术研究进展[J]. 纺织学报, 2020, 41(10): 178-187.
[3] 刘稀, 王冬, 张丽平, 李敏, 付少海. 低折射率树脂对原液着色粘胶纤维结构和性能的影响[J]. 纺织学报, 2020, 41(07): 9-14.
[4] 许黛芳. 磷酸改性芳纶对聚氨酯硬质泡沫阻燃抑烟性能的影响[J]. 纺织学报, 2020, 41(05): 30-37.
[5] 马君志, 王冬, 付少海. 氧化石墨烯协同二硫代焦磷酸酯阻燃粘胶纤维的制备及其性能[J]. 纺织学报, 2020, 41(03): 15-19.
[6] 党丹旸, 崔灵燕, 王亮, 刘雍. 纤维素纳米纤维/ 纳米蒙脱土复合气凝胶制备及其结构与性能[J]. 纺织学报, 2020, 41(02): 1-6.
[7] 尹思力, 杨洋, 江文, 石业新, 周小华, 黄金洪. 接枝蚕蛹肽羧基化粘胶纤维的制备及其优化工艺[J]. 纺织学报, 2019, 40(08): 14-19.
[8] 吴娇, 于湖生, 万兴云, 田平, 李慧敏, 侯晓欣. 抗菌防螨防霉功能改性粘胶纤维的制备及其性能[J]. 纺织学报, 2019, 40(07): 19-23.
[9] 莫达杰, 李旭明, 许增慧. 聚(3-羟基丁酸-co-3-羟基戊酸共聚酯)/聚乳酸阻燃纤维的制备及其性能[J]. 纺织学报, 2019, 40(05): 12-17.
[10] 张安莹, 王照颖, 王锐, 董振峰, 魏丽菲, 王德义. 阻燃聚左旋乳酸及其纤维的制备与结构性能[J]. 纺织学报, 2019, 40(04): 7-14.
[11] 赵青华, 毛秦岑, 梅涛, 牛应买, 王栋. 阻燃剂对聚氯乙烯/聚酯复合材料性能的影响[J]. 纺织学报, 2019, 40(01): 103-107.
[12] 卢琳娜 陈宇岳 李永贵. 纳米金与粘胶纤维的吸附机制[J]. 纺织学报, 2018, 39(09): 22-28.
[13] 刘婷 张安莹 王锐 董振峰 朱志国 王照颖. 季戊四醇磷酸酯/二乙基次磷酸锌协同阻燃聚酰胺6的制备及其性能 [J]. 纺织学报, 2018, 39(09): 8-14.
[14] 姚萍 江文 王江 黄金洪 周小华. 接枝壳寡糖抗菌粘胶纤维的制备及其抗菌性与染色效果[J]. 纺织学报, 2018, 39(04): 9-13.
[15] 邓继勇 柳芊 董新理 汪南方. 新型氮-磷阻燃剂制备及其对棉织物的阻燃性能[J]. 纺织学报, 2017, 38(11): 97-101.
Viewed
Full text


Abstract

Cited

  Shared   
  Discussed   
No Suggested Reading articles found!