CN110205821A - 一种绿色无氟防水整理剂及其在纤维制品中的应用 - Google Patents
一种绿色无氟防水整理剂及其在纤维制品中的应用 Download PDFInfo
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Abstract
本发明公开了一种绿色无氟防水整理剂及其在纤维制品中的应用。所述的整理剂由苯乙硫醚丙基巯丙基聚倍硅氧烷、苯乙硫醚甲基丙烯酰氧丙基梯形聚有机硅树脂、十六烷基三甲基溴化铵、(3‑巯丙基)三甲氧基硅烷、苯乙硫醚甲基丙烯酰氧丙基梯形聚有机硅树脂/SiO2溶胶、光引发剂、硅氧烷基甲基丙烯酸酯、十二烷基硫酸钠、脂肪酸聚氧乙烯醚、过硫酸铵、甲基丙烯酸甲酯和甲基丙烯酸羟乙酯组成。所述整理剂应用于纤维制品中。本发明克服了现有产品的不足,易于工业化生产,应用方法简单,成本低,具有良好的应用前景和经济效益。
Description
技术领域
本发明属于纺织化学品制备及其应用领域,具体涉及一种绿色无氟防水整理剂及其在纤维制品中的应用。
背景技术
随着生活水平的日益提高,人们对服装面料各方面的要求也越来越高,个性化、高档化及吸湿、透气、排汗、快干、防臭抗菌、抗紫外线等功能性纺织品己成为纺织服装面料的发展趋势。防水拒油、易去污多功能整理可显著改善织物的表面性能,使织物不易被水、油、咖啡等污渍润湿和沾污。在众多的防水整理剂中,含氟防水剂在织物上应用后的效果最为明显,但大多织物含氟防水剂产品均含有PFOS。目前应用最广泛的拒水拒油整理剂是含氟的有机聚合物,此类拒水剂既有卓越的拒水性能又有良好的拒油性能,耐久性好,而且不影响纤维原有的风格,因而受到消费者的青睐。然而拒水整理剂在纺织品加工工艺中应用广泛,常用的拒水整理剂为含氟丙烯酸酯共聚物乳液。但含氟类化合物价格昂贵,且生产含氟整理剂过程中的助剂为全氟辛酸及其盐类(PFOA)和全氟辛烷磺酸(PFOS),它们具有潜在的致癌性,在整理中和整理后会释放氟化合物,危害人体和环境。由于PFOA和PFOS是一种化学稳定性极高的化合物,在环境中具有很高的持久性,并且会在环境中聚集,在生物体内积累,很难通过新陈代谢而分解生产和整理过程中广泛使用的全氟辛酸及其盐类(PFOA)、全氟辛磺酸(PFOS)等长碳链化学品具有生物毒性和环境污染。鉴于此,寻找和开发无氟防水产品和防水技术迫在眉睫。与含氟化合物相比,有机硅拒水整理剂的优点众多,如环境友好、成本低廉,且具有很好的耐热性、耐候性和抗紫外性能等,但有机硅也存在机械强度不足、附着力差等不足之处。UV紫外光固化整理剂由于具有固化速度快、对环境污染小、节省能源、对基材的适用范围广以及适合于高速自动化生产等优点而日益受到重视。但以往UV固化整理剂使用的低聚物主要为线形聚合物,存在粘度大、氧阻聚较严重等问题。为得到应用所需的粘度和流变性能,需要加入大量的稀释剂来调节,且使用的稀释剂大多有刺激性气味且易挥发,容易对人体健康和周围环境造成伤害,限制了其应用。
发明内容
为解决现有技术的缺点和不足之处,本发明的首要目的在于提供一种绿色无氟防水整理剂。
本发明的另一目的在于提供上述一种绿色无氟防水整理剂在纤维制品中的应用。
本发明目的通过以下技术方案实现:
一种绿色无氟防水整理剂,包含以下质量百分数的组分:
10~20%组分A、10~20%组分B和60~80%组分C;
其中,组分A由质量比为(1~2):(4~6):(2~3):(0.5~1)的苯乙硫醚丙基巯丙基聚倍硅氧烷、苯乙硫醚甲基丙烯酰氧丙基梯形聚有机硅树脂、十六烷基三甲基溴化铵和(3-巯丙基)三甲氧基硅烷组成;
组分B由质量比为(15~40):1的苯乙硫醚甲基丙烯酰氧丙基梯形聚有机硅树脂/SiO2溶胶和光引发剂组成;
组分C由质量比为(4~5):(0.03~0.06):(0.03~0.06):(0.015~0.03):(1~2):(0.5~1)的硅氧烷基甲基丙烯酸酯、十二烷基硫酸钠、脂肪酸聚氧乙烯醚、过硫酸铵、甲基丙烯酸甲酯和甲基丙烯酸羟乙酯组成;
上述组分A、B和C的质量百分数之和为100%。
所述苯乙硫醚甲基丙烯酰氧丙基梯形聚有机硅树脂/SiO2溶胶中苯乙硫醚甲基丙烯酰氧丙基梯形聚有机硅树脂与SiO2溶胶的摩尔比为1:16~1:21。
所述的光引发剂优选为DAROCUR 1173、IRGACURE 2100和IRGACURE 2959中的至少一种。
所述的硅氧烷基甲基丙烯酸酯优选为二硅氧烷基甲基丙烯酸酯。
所述的脂肪酸聚氧乙烯醚优选为十二烷基聚氧乙烯醚、十六烷基聚氧乙烯醚和十八烷基聚氧乙烯醚中的至少一种。
上述一种绿色无氟防水整理剂的制备方法为:将绿色无氟防水整理剂各组分按照比例混合均匀,制得绿色无氟防水整理剂。
上述一种绿色无氟防水整理剂在纤维制品中的应用。
所述的纤维制品为由纤维素纤维、蛋白质纤维和合成纤维中的至少一种纤维制得的机织物、针织物或非织造布。
所述一种绿色无氟防水整理剂在纤维制品中的应用,具体方法为:将绿色无氟防水整理剂与水混合配制成浓度为5~30g/L的整理液,然后浸轧纤维制品,紫外光固化。
所述的浸轧条件优选为:先浸润30min,再二浸二轧(室温),轧余率为30-75wt%。
所述的二浸二轧是指纤维制品浸润整理液30min后经轧辊轧过,再重复浸轧一次。
所述紫外光固化的时间优选为1~3min。
与现有技术相比,本发明具有以下优点及有益效果:
(1)本发明克服了现有产品的不足,能实现纤维制品拒水拒油,易于工业化生产,应用方法简单,成本低,防水性能优异,低碳节能,具有良好的应用前景和经济效益。
(2)本发明利用具有高度支化分子拓扑结构的树形超支化聚合物制备整理剂,由于其具有分子间链缠结少、溶解性好、粘度低、易成膜和反应活性高等特点,克服了线形低聚物制得的整理剂粘度大、氧阻聚较严重的缺点。
(3)本发明结合有机硅和丙烯酸酯的各自优势,利用环境友好型有机硅氧烷基和长碳链烷基提供拒水功能,制备一类不含氟元素的光固化拒水整理剂,为制备绿色环保的拒水整理剂奠定基础。
具体实施方式
下面结合实施例对本发明作进一步详细的描述,但本发明的实施方式不限于此。
本申请实施例所用DAROCUR1173购买于Sigma-Aldrich公司。
所用二硅氧烷基甲基丙烯酸酯合成参见专利CN101497682A。
所用十八烷基聚氧乙烯醚(93)、十六烷基聚氧乙烯醚(C10)和十二烷基聚氧乙烯醚(L4)均购买于Sigma-Aldrich公司。
所用苯乙硫醚丙基巯丙基聚倍硅氧烷是通过硫-烯点击反应将苯乙烯修饰到POSS-SH8上制得,具体方法为:
称取POSS-SH8(0.01mol,9.3g)溶解在20mL二氯甲烷溶液中作为A液;称取苯乙烯(4.16g,0.04mol)和光引发剂Irgacure-907(0.02g,购买于常州强力公司)溶解在20mL二氯甲烷溶液中作为B液。首先将A液转移到带有磁力搅拌装置的单口烧瓶中,开启搅拌并用365nm波长的LED紫外光源进行照射;随后,将B液转移到用铝箔进行避光处理的恒压滴液漏斗中,B液以一定的速度地加入A液中,滴加完成时间控制在半小时左右。B液滴加完成后,混合液在紫外光下继续曝光搅拌2小时。旋转蒸馏除去二氯甲烷溶剂后得到透明粘稠液体物质,用甲醇溶液反复洗涤,最后将之置于真空干燥箱内,70℃下干燥24小时,即得目标产物。(制备方法详见:甘延长.仿生图案化光固化涂层的制备及其应用研究[D].上海交通大学,2015,其中POSS-SH8的制备方法详见:Lin,H;Wan,X;Jiang,X S;Wang,Q K;Yin,J,Ananoimprint lithography hybrid photoresist based on the thiol-enesystem.Adv.Funct.Mater.:2011,21,2960-2967)。
本申请实施例所用苯乙硫醚甲基丙烯酰氧丙基梯形聚有机硅树脂的制备方法如下:
首先通过点击化学反应将苯乙烯点击到巯丙基三甲氧基硅烷上合成苯乙硫醚丙基三甲氧基硅烷(St-TMS):称取(3-巯基丙基)三甲氧基硅烷(MTPS,9.26g,0.047mol,购买于百灵威试剂公司)溶解在20mL二氯甲烷溶液中作为A液;称取苯乙烯(4.9g,0.047mol)和光引发剂I-907(20mg)溶解在20mL二氯甲烷溶液中作为B液。首先将A液转移到带有磁力搅拌装置的单口烧瓶中,开启搅拌并用365nm波长的LED紫外光源进行照射;随后,将B液转移到用铝箔进行避光处理的恒压滴液漏斗中,B液以一定的速度地加入A液中,滴加完成时间控制在半小时左右。B液滴加完成后,混合液在紫外光下继续曝光搅拌2小时,-0.1Mpa压力下旋转蒸馏除去二氯甲烷溶剂得到产物St-TMS。(详见:甘延长.仿生图案化光固化涂层的制备及其应用研究[D].上海交通大学,2015)。
苯乙硫醚甲基丙烯酰氧丙基梯形聚有机硅树脂(LPSQ)在碱性条件下用St-TMS和MA-TMS(3-(甲基丙烯酰氧)-丙基三甲氧基硅烷,购买于百灵威试剂公司)共水解得到:称取去离子水(2.4g,0.133mol)和K2CO3(0.02g,0.145mol)搅拌混合均匀后,加入四氢呋喃(4.0g,0.056mol)搅拌30分钟。然后加入St-TMS(0.04mol)和MA-TMS(0.04mol)混合溶液,通氮气保护,室温下搅拌反应96小时,静置数小时后,将上层溶液倒去,得到粘稠状物质。加入30mL二氯甲烷溶解,再用去离子水洗涤萃取5次。分离出二氯甲烷相,浓缩到10mL左右加入100mL冰甲醇溶液,充分搅拌后,混合液置于-5℃环境静置3小时,倒去上层甲醇溶液得到粘稠透明物质,-0.1MPa压力下40℃旋转蒸馏除去小分子即得到透明粘稠产物。
SiO2溶胶的制备方法参考:肖轶群,谢志勇,沈军,et al.溶胶-凝胶工艺制备SiO2薄膜的结构控制和稳定性研究[J].强激光与粒子束,2006,18(8):1302-1306。以正硅酸乙酯(TEOS)为前驱体,氨水或HCl为催化剂,分别在碱性和酸性条件下制备SiO2溶胶。溶胶的配制过程应在干净清洁、相对湿度小于60%的环境下进行。
碱性催化溶胶的配制过程是将TEOS、氨水(pH=12)和无水乙醇按照物质的量之比1∶2∶40混合搅拌均匀后,放置在稳定环境(20℃,相对湿度20%)下静置老化4d,溶胶呈现淡蓝色乳胶状。将老化后的碱性溶胶在80℃下回流10h,除去溶胶中的催化剂氨,以防止溶胶进一步水解缩聚。
SiO2溶胶制备完成后均放置在4℃的冰柜中存贮,以保持溶胶的相对稳定。
实施例1
一种绿色无氟防水整理剂,按以下质量百分比组成:
10%组分A、10%组分B和80%组分C;
其中,组分A为质量比为1:4:2:0.5的苯乙硫醚丙基巯丙基聚倍硅氧烷、苯乙硫醚甲基丙烯酰氧丙基梯形聚有机硅树脂、十六烷基三甲基溴化铵和(3-巯丙基)三甲氧基硅烷组成的混合物;
组分B为质量比为40:1的苯乙硫醚甲基丙烯酰氧丙基梯形聚有机硅树脂/SiO2溶胶和光引发剂组成的混合物;
组分C为质量比为4:0.03:0.03:0.015:1:0.5的1,1,3,3-四甲基二硅氧烷基甲基丙烯酸酯、十二烷基硫酸钠、十八烷基聚氧乙烯醚、过硫酸铵、甲基丙烯酸甲酯、甲基丙烯酸羟乙酯组成的混合物;
苯乙硫醚甲基丙烯酰氧丙基梯形聚有机硅树脂/SiO2溶胶中苯乙硫醚甲基丙烯酰氧丙基梯形聚有机硅树脂和SiO2溶胶的摩尔比为1:16,光引发剂为DAROCUR 1173。
待整理的织物为质量比为棉:涤(70:30)混纺面料。
将上述绿色无氟防水整理剂各组成按照比例混合均匀,制得绿色无氟防水整理剂;将绿色无氟防水整理剂与水混合配制成浓度为10g/L的整理液,浸轧纤维制品,紫外光固化。
其中,工艺流程为:用整理液浸润织物30min→二浸二轧(每次浸润30min,轧余率为70wt%,室温)→紫外光固化1min,得到整理剂整理过后的织物。
实施例2
一种绿色无氟防水整理剂,按以下质量百分比组成:
15%组分A、15%组分B和70%组分C;
其中,组分A为质量比为1.5:5:2.5:0.75的苯乙硫醚丙基巯丙基聚倍硅氧烷、苯乙硫醚甲基丙烯酰氧丙基梯形聚有机硅树脂、十六烷基三甲基溴化铵和(3-巯丙基)三甲氧基硅烷组成的混合物;
组分B为质量比为30:1的苯乙硫醚甲基丙烯酰氧丙基梯形聚有机硅树脂/SiO2溶胶和光引发剂组成的混合物;
组分C为质量比为4.5:0.045:0.045:0.015:1.5:0.75的1,1,3,3-四甲基二硅氧烷基甲基丙烯酸酯、十二烷基硫酸钠、十二烷基聚氧乙烯醚、过硫酸铵、甲基丙烯酸甲酯、甲基丙烯酸羟乙酯组成的混合物;
苯乙硫醚甲基丙烯酰氧丙基梯形聚有机硅树脂/SiO2溶胶中苯乙硫醚甲基丙烯酰氧丙基梯形聚有机硅树脂和SiO2溶胶的摩尔比为1:16,光引发剂为DAROCUR 1173。
待整理的织物为质量比为羊毛:涤(60:40)混纺面料。
将上述绿色无氟防水整理剂各组成按照比例混合均匀,制得绿色无氟防水整理剂;将绿色无氟防水整理剂与水混合配制成整理液,整理液浓度为10%,浸轧纤维制品,紫外光固化。
其中,工艺流程为:用整理液浸润织物30min→二浸二轧(每次浸润30min,轧余率为70wt%,室温)→紫外光固化2min,得到整理剂整理过后的织物。
实施例3
一种绿色无氟防水整理剂,按以下质量百分比组成:
20%组分A、20%组分B和60%组分C;
其中,组分A为质量比为2:6:3:1的苯乙硫醚丙基巯丙基聚倍硅氧烷、苯乙硫醚甲基丙烯酰氧丙基梯形聚有机硅树脂、十六烷基三甲基溴化铵和(3-巯丙基)三甲氧基硅烷组成的混合物;
组分B为质量比为15:1的苯乙硫醚甲基丙烯酰氧丙基梯形聚有机硅树脂/SiO2溶胶和光引发剂组成的混合物;
组分C为质量比为5:0.06:0.06:0.03:2:1的1,1,3,3-四甲基二硅氧烷基甲基丙烯酸酯、十二烷基硫酸钠、十六烷基聚氧乙烯醚、过硫酸铵、甲基丙烯酸甲酯、甲基丙烯酸羟乙酯组成的混合物;
苯乙硫醚甲基丙烯酰氧丙基梯形聚有机硅树脂/SiO2溶胶中苯乙硫醚甲基丙烯酰氧丙基梯形聚有机硅树脂和SiO2溶胶的摩尔比为1:16,光引发剂为DAROCUR 1173。
待整理的织物为质量比为麻:棉(30:70)混纺面料。
将上述绿色无氟防水整理剂各组成按照比例混合均匀,制得绿色无氟防水整理剂;将绿色无氟防水整理剂与水混合配制成浓度为10%的整理液,浸轧纤维制品,紫外光固化。
其中整理工艺流程为:用整理液浸润织物30min→二浸二轧(每次浸润30min,轧余率为70wt%,室温)→紫外光固化3min,得到整理剂整理过后的织物。
本发明样品的机械强度测定:按照美国材料与试验协会标准ASTM D5034-95的规定,使用拉伸测试仪测定织物的纬向拉伸强力(断裂强力)。首先在每一块待测织物上裁取试样,大小为100×200mm,其长边平行于纬向,将所有试样置于温度为21±1℃,湿度为65±2%的标准环境中预先调湿24小时,并在此标准环境中进行测试;将试样安装到测试仪上,使长边平行于拉力的方向,中线位于两个夹钳的中央,锁定夹钳,启动测试仪匀速缓慢拉伸试样,直至试样断裂记录下此时的拉力数值。重复测试试样取拉力的平均数值。
纬向拉伸强力保留率计算公式如下:
BR=BS/BS0×100%
式中BS-整理后织物的拉伸强力(1b)
BS0-未整理织物的拉伸强力(1b)
表1样品的力学性能
本发明对整理剂整理过后的织物的拒水性能主要是通过接触角测试、喷淋性能测试来评定的。
接触角测试为:剪取整理后织物布样1cm×1cm,在DSA-30型接触角性能测试仪器上测试。
拒水性能测试按AATCC-22标准(参照我国的GB4745-84《纺织织物表面抗湿性测定方法》)在YB813型织物沾水度测定仪(温州大荣纺织标准仪器厂)上测试。用标准沾湿卡评分,淋水仪上进行淋水实验。
表2织物的拒水性能
实施例 | 接触角(°) | 喷淋评分(分) |
1 | 130.5 | 70 |
2 | 127.9 | 68 |
3 | 133.6 | 74 |
接触角大小反应了表面的亲水亲油性,角度越大越疏水,由于是做纺织织物表面抗湿性的测定,所以接触角越大、评分越高抗湿性越好。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
1.一种绿色无氟防水整理剂,其特征在于,包含以下质量百分数的组分:
10~20%组分A、10~20%组分B和60~80%组分C;
其中,组分A由质量比为(1~2):(4~6):(2~3):(0.5~1)的苯乙硫醚丙基巯丙基聚倍硅氧烷、苯乙硫醚甲基丙烯酰氧丙基梯形聚有机硅树脂、十六烷基三甲基溴化铵和(3-巯丙基)三甲氧基硅烷组成;
组分B由质量比为(15~40):1的苯乙硫醚甲基丙烯酰氧丙基梯形聚有机硅树脂/SiO2溶胶和光引发剂组成;
组分C由质量比为(4~5):(0.03~0.06):(0.03~0.06):(0.015~0.03):(1~2):(0.5~1)的硅氧烷基甲基丙烯酸酯、十二烷基硫酸钠、脂肪酸聚氧乙烯醚、过硫酸铵、甲基丙烯酸甲酯和甲基丙烯酸羟乙酯组成;
上述组分A、B和C的质量百分数之和为100%。
2.根据权利要求1所述一种绿色无氟防水整理剂,其特征在于,所述苯乙硫醚甲基丙烯酰氧丙基梯形聚有机硅树脂/SiO2溶胶中苯乙硫醚甲基丙烯酰氧丙基梯形聚有机硅树脂与SiO2溶胶的摩尔比为1:16~1:21。
3.根据权利要求1或2所述一种绿色无氟防水整理剂,其特征在于,所述硅氧烷基甲基丙烯酸酯为二硅氧烷基甲基丙烯酸酯。
4.根据权利要求3所述一种绿色无氟防水整理剂,其特征在于,所述脂肪酸聚氧乙烯醚为十二烷基聚氧乙烯醚、十六烷基聚氧乙烯醚和十八烷基聚氧乙烯醚中的至少一种。
5.根据权利要求3所述一种绿色无氟防水整理剂,其特征在于,所述光引发剂为DAROCUR 1173、IRGACURE 2100和IRGACURE 2959中的至少一种。
6.权利要求1~5任一项所述一种绿色无氟防水整理剂在纤维制品中的应用。
7.根据权利要求6所述一种绿色无氟防水整理剂在纤维制品中的应用,其特征在于,所述纤维制品为由纤维素纤维、蛋白质纤维和合成纤维中的至少一种纤维制得的机织物、针织物或非织造布。
8.根据权利要求6或7所述一种绿色无氟防水整理剂在纤维制品中的应用,其特征在于,具体方法为:将绿色无氟防水整理剂与水混合配制成浓度为5~30g/L的整理液,然后浸轧纤维制品,紫外光固化。
9.根据权利要求8所述一种绿色无氟防水整理剂在纤维制品中的应用,其特征在于,所述浸轧条件为:先浸润30min,再二浸二轧,轧余率为30-75wt%。
10.根据权利要求8所述一种绿色无氟防水整理剂在纤维制品中的应用,其特征在于,所述紫外光固化时间为1~3min。
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