CN112127157A - 一种聚氨基酸接枝改性拒水织物及其制备方法 - Google Patents
一种聚氨基酸接枝改性拒水织物及其制备方法 Download PDFInfo
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- CN112127157A CN112127157A CN202011043939.8A CN202011043939A CN112127157A CN 112127157 A CN112127157 A CN 112127157A CN 202011043939 A CN202011043939 A CN 202011043939A CN 112127157 A CN112127157 A CN 112127157A
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
本发明公开了一种聚氨基酸接枝改性拒水织物及其制备方法。在纤维表面接入氨基,由氨基引发苯胺基酸酐在纤维表面开环聚合形成接枝链,制得一种纤维表面聚氨基酸改性的拒水织物。本发明织物处理是在液相中以纤维表面预先接入的氨基为引发剂,通过开环聚合法(ROP)引发(取代)苯胺基酸酐在纤维表面完成接枝聚合,生产条件温和,产品制备工艺简单及操作安全。公开的以化学接枝得到的拒水织物,纤维表面功能防护层以共价键与纤维结合,具有优异的牢度,且不影响织物的服用性能,解决了通过涂层等方法获得拒水织物牢度差的难题。接枝改性所采用的疏水性聚氨基酸属于生物相容性好、可自然降解的环保型聚合物,符合当前大力开发绿色纺织品的趋势。
Description
技术领域
本发明涉及一种拒水织物及其制备方法,具体涉及一种聚氨基酸接枝改性的织物,属于特种功能性纺织品及其制备技术领域。
背景技术
随着人们生活水平的提高,人们对现代纺织品的要求也越来越高,因此纺织品逐渐功能化,例如:希望纺织品具有防水、防风、抗菌、抗紫外等功能。为了满足人们对纺织品的需求,必须对一些天然纤维或者人造纤维进行表面改性以使纺织品功能化。
目前针对纤维表面改性主要包括:物理改性和化学改性。物理改性主要有γ辐射诱导、表面涂层、超声波浸渍及等离子体处理等,而化学改性根据作用的方式不同大体分为表面刻蚀和表面接枝(原子转移自由基聚合等)。其中,γ辐射诱导、原子转移自由基聚合等处理方法存在着操作难度大、工艺复杂、设备要求苛刻,成本高且容易损伤纤维的问题。与之相比,通过在织物表面进行涂层改性,方法工艺简单、操作更容易,主要就是将一层或者多层能形成薄膜的高分子化合物均匀的涂覆在织物的表面,然而,涂层发处理织物获得的聚水功能耐久性不好。
发明内容
本发明将开环聚合法用于纤维材料的表面改性,公开了一种聚氨基酸接枝改性的拒水织物及其制备方法,使纤维表面引发诱导苯胺基酸酐单体开环聚合,通过控制处理工艺,在保证织物(或纤维)的强力、透气性、白度、手感等性能不受影响的前提下,获得一种表面疏水改性的织物。针对目前拒水性织物普遍存在的耐久性不理想的问题,本发明形成疏水接枝链,从而能够提供拒水功能,且拒水性耐久。
实现本发明目的的技术方案是:
一种聚氨基酸接枝改性拒水织物,所述聚氨基酸接枝改性拒水织物包括织物以及织物表面的聚氨基酸接枝链;所述聚氨基酸接枝链的化学结构如下:
其中, R1、R2、R3独立的选自H、-CH3、-CH2CH3 或-CF3;R4为-CH3或-CH2CH3;R5为-CH2-或-CH2CH2CH2NH-;X为O或NH;n=3~200。
本发明织物为棉织物、麻织物、毛织物、真丝织物中的一种或者几种;织物中纤维为棉、麻、毛、真丝等中的任意一种或几种,对其进行聚氨基酸接枝改性。
上述聚氨基酸接枝改性拒水织物的制备方法包括以下步骤,将氨基预处理织物与苯胺基酸酐混合反应,得到所述聚氨基酸接枝改性拒水织物;所述苯胺基酸酐如下:
其中,R1、R2、R3独立的选自H、-CH3、-CH2CH3 或-CF3;R4为-CH3或-CH2CH3。
本发明中,在反应器中加入氨基预处理织物,再加入苯胺基酸酐,在纤维表面引发进行开环聚合反应,接枝改性纤维;所述反应的温度为0~80℃,最好为室温~70℃,时间为1~120h,最好为24~60h;优选的,所述反应温度为四级阶梯升温,比如室温+(30~50℃)+(50~60℃)+(60~70℃),相邻阶梯温度相差5~25℃。
进一步的,纤维表面开环聚合结束后,取出改性后的织物,放入水中洗涤,再干燥,得到聚氨基酸接枝改性拒水织物。
本发明中,所述氨基预处理织物为氨基硅烷偶联剂处理的织物。将氨基硅烷偶联剂在水/乙醇混合溶剂中水解得到水解液,将织物投入水解液中反应,得到纤维表面具有氨基的预处理织物,为氨基预处理织物;氨基硅烷偶联剂为氨丙基三乙氧基硅烷、氨丙基三甲氧基硅烷、氨乙胺丙基三乙氧基硅烷、氨乙胺丙基三甲氧基硅烷中的任意一种;水和乙醇的体积比为1:4~20,最好为1:8~10,氨基硅烷偶联剂用量为织物重量的0.5~20%,最好为5~15%;水解时间为0.1~24h,最好为1~12h;水解温度为5~45℃,最好为20~30℃;水解所需的PH值为7~11,最好为8~10,可以用常规氨水调节。反应的温度为室温~100℃,最好为50~60℃;反应的时间为30 min ~24h,最好为1h~3h。
本发明中,氮气保护下,N-苯基-叔丁氧碳基甘氨酸环化反应,得到苯胺基酸酐;所述N-苯基-叔丁氧碳基甘氨酸如下:
其中,R1、R2、R3独立的选自H、-CH3、-CH2CH3 或-CF3;R4为-CH3或-CH2CH3。
具体的,将N-苯基-叔丁氧碳基甘氨酸溶解在无水溶剂中,在氮气保护下加入环合剂,再进行环化反应,生成苯胺基酸酐;环合剂为PCl3;所述无水溶剂为无水二氯甲烷、无水三氯甲烷或无水四氯乙烷;优选分2~10批加入环合剂,最好为分3~5批,加入环合剂的温度为-20~45℃,最好为-5~5℃;环化反应的温度为5~45℃,最好为20~30℃;时间为0.1~48h,最好为12~24h。
本发明中,在缚酸剂存在下,N-苯基氨基酸与Boc酸酐反应,得到N-苯基-叔丁氧碳基甘氨酸;所述缚酸剂为三乙胺或吡啶;所述反应的温度为5~45℃,时间为0.1~24h。进一步的,N-苯基氨基酸与Boc酸酐的摩尔比为1:2.5。优选的,将Boc酸酐溶液滴加至N-苯基氨基酸溶液与缚酸剂的混合物中,进行加成-消去反应,得到N-苯基-N-叔丁氧羰基甘氨酸;Boc酸酐溶液的滴加时间为20~120min,最好为30~60min。N-苯基氨基酸溶液中,溶剂为水/1,4-二氧六环,其中水和二氧六环的体积比为1:1~2,最好为1:1~1.5;Boc酸酐溶液中,溶剂为1,4-二氧六环、四氢呋喃或乙醚中的任意一种。N-苯基氨基酸与Boc酸酐反应的反应温为5~45℃,最好为室温;反应的时间为0.1~24h,最好为12~18h。
本发明公开了上述聚氨基酸接枝改性拒水织物在制备拒水材料中的应用;所述拒水材料具有耐洗性与降解性。
与现有技术相比,本发明提供的技术方案其有益效果在于:
(a)本发明聚氨基酸接枝改性拒水织物中,通过共价键与纤维连接,从而赋予疏水性织物优异的耐久牢度,解决了常规涂层通过物理作用固着织物而牢度查的问题以及其它物理改性所带来的成本高、设备要求苛刻等问题。
(b)本发明所采用的聚合方法是开环聚合法(ROP),含苯胺基酸酐单体在纤维表面开环聚合的聚合度可以通过调整工艺进行控制,开环聚合所获得的聚合物的分子量可控制,因此纤维表面性能易于控制。
(c)对天然纤维织物接枝改性所采用的聚氨基酸属于生物相容性好、可自然降解的环保型聚合物,符合当前绿色纺织品开发的趋势。
(d)本发明中制备的疏水性织物的制备方法为“一浴法”,原料成本低、环保,制备工艺简单、条件温和,易于工业化生产和推广。
附图说明
图 1 是实施例一制备得到的N-(p-三氟甲苯)胺基酸酐在纤维表面开环聚合接枝改性棉织物,并皂洗后扫描电子显微镜(SEM)图(左);皂洗后接触角测试图(右上)表明,织物对水接触角为141.6°,处理织物疏水性优良,表面涂层皂洗稳定,耐久性很好。
图2是实施例二制备的N-苯胺基酸酐氢核磁图,溶剂为氘代氯仿;
图3是实施例二制备的N-苯胺基酸酐红外图;
图4是实施例二制备得到的聚苯基氨基酸接枝改性织物FT-IR图,从红外吸收曲线中出现的苯环和氨基酸结构特征吸收峰可知,聚苯基氨基酸已成功接入麻纤维表面。
图5是实施例二制备得到的N-苯胺基酸酐在麻纤维表面开环聚合整理织物皂洗后接触角测试图,可知织物对水接触角为140.1°,处理织物疏水性优良得到表面涂层皂洗稳定,耐久性很好。
图6是实施例三制备得到的N-苯胺基酸酐在丝织物表面开环聚合整理织物皂洗后接触角测试图,测得织物对水接触角为139.8°,处理丝织物疏水性良好。
图7是实施例三制备得到的聚氨基酸接枝改性真丝织物和经市售拒水整理剂整理丝织物,在蛋白酶催化降解后的光学照片,可见聚苯基氨基酸接枝改性真丝织物易降解,而市售拒水整理剂整理丝织物在该条件下基本不降解。
具体实施方式
本发明公开了上述疏水性织物的制备方法,包括如下步骤:
加成-消去反应:N-苯基氨基酸在混合溶剂中与Boc酸酐发生加成-消去反应,形成中间体N-苯基-叔丁氧碳基甘氨酸;
PCl3 环合:N-苯基-叔丁氧碳基甘氨酸在环合剂PCl3 的作用下,由羧基与Boc基成环,生成N-苯胺基酸酐;
织物预处理:将织物用氨基硅烷偶联剂水解液预先处理,在织物纤维表面引入活性氨基;
其中,R4= -CH3 或 -CH2CH3 ; R5= -CH2-或 -CH2CH2CH2NH-;X = -O- 或 -NH-;
开环聚合:在纤维表面,诱导N-苯胺基酸酐单体开环聚合,形成接枝链;
其中, R1, R2, R3= -H,-CH3, - CH2CH3 或 -CF3 ;
R4= -CH3 或 -CH2CH3 ;
R5= -CH2-或 -CH2CH2CH2NH-;
X = -O- 或 -NH-;
n=3~200。
取出改性后的织物,放入水中洗涤、干燥,得到一种聚氨基酸接枝改性的疏水织物。
本发明涉及的原料都是市售常规产品,具体制备方法以及测试操作都为常规方法,如无特殊说明,都在室温、常规环境中进行,用于氨基预处理的织物为常规织物,未处理,具有亲水性。
下面结合附图和实施例对本发明技术方案做进一步描述。
实施例一
(1)生成N-三氟甲苯基-N-叔丁氧羰基甘氨酸
2500mL单口烧瓶,配备磁力搅拌器。取52g N-三氟甲苯基氨基乙酸于800mL的水/1,4-二氧六环的混合溶液(水和二氧六环的体积比为1:1)中溶解至完全透明,再用注射器加入184mL的三乙胺溶液,滴加含有142g Boc酸酐的400mL 1,4-二氧六环溶液,40min滴加完成。反应在室温下搅拌16h后,用500mL正己烷萃取两次,再加入800mL的1 N HCl溶液使其呈酸性,再用2×300mL乙酸乙酯溶液萃取产物。合并有机相,用800mL的盐水洗涤有机层,去离子水水洗三次,无水硫酸镁干燥,过滤,减压蒸馏除去溶剂,得45.3g黑褐色粘稠状产物,产率61.1%。
(2)生成N-三氟甲苯胺基酸酐
在氮气氛围下,将上述(1)所得产物溶于900mL的无水二氯甲烷溶液中,将溶液在低温反应釜中冷却至0℃,通过注射器将46.0g的PCl3溶液分三批(16g+15g+15g)加入到反应液中,间隔15min,反应液在0℃下搅拌1h,然后转移至室温下反应15小时。真空除去溶剂,将所得固体再溶于300mL的无水二氯甲烷,过滤,滤液蒸发后可得到约23.3g淡黄色粗产物固体,产率69%。将23.0g淡黄色固体在无水二氯甲烷/正己烷的混合溶液中进行重结晶,最后可得用于聚合的12.9g白色固体产物N-(p-三氟甲苯)胺基酸酐,产率49.1%。
(3)织物的预处理:
将氨基硅烷偶联剂氨丙基三乙氧基硅烷溶于水/乙醇的混合溶液(水和乙醇的体积比为1:9)中,用10%的氨水调节溶液pH至10,在室温下水解3h得到氨基硅烷偶联剂透明水解液,然后将一块300g圆形棉织物于上述400mL氨基硅烷偶联剂水解液中(氨基硅烷偶联剂用量为织物重量的6%)进行水浴反应,水浴温度50℃,反应时间为120min。反应完成后,取出织物,水洗三次,60℃烘干,120℃焙烘3min,得到预处理棉织物。
(4)制备拒水性织物:
取3.1g步骤(2)中的白色固体产物N-三氟甲苯胺基酸酐于450mL的N,N-二甲基甲酰胺(DMF)溶液中完全溶解,将预处理后的织物加入到DMF的溶液中,在室温下反应4h,后升温至50℃反应8h,再升温至60℃反应12h,最后升温至70℃反应12h,总接枝反应时间为48h。反应完成后,取出织物终止反应,水洗三次,常规超声波清洗15min,再60℃烘干,得到拒水性棉织物,结构示意图见图1,纤维表面接枝链结构如下(波浪线为纤维,n为20~60):
(5)皂洗牢度测试
处理布样按照GB/T 3921-2008《纺织品色牢度实验耐皂洗色牢度》进行皂洗后,测试接枝改性的皂洗耐久性。
(6)接触角测试
接触角测试采用德国Krüss公司的DSA100型全自动微观液滴润湿性测量仪对皂洗前后的涂层织物润湿性能测试,选取水作为测试液滴,液滴体积为5μL,分别测试五次取其平均值。测得皂洗前后酸酐开环聚合法整理织物表面接触角分别为145.4°和141.6°,皂洗后仍能表现出疏水性能,表明整理耐久性好。
(7)降解性测试
拒水织物样品剪成直径大约10 mm的圆片,并依次以乙醇、去离子水清洗后,37℃下真空烘干24 h,备用。使用木瓜蛋白酶(Papain)作蛋白水解酶,蛋白酶在0.01M半胱氨酸,0.04M EDTA缓冲溶液中活化(pH8.0),浓度为lmg酶/ml溶液。使用移液管移取3mL酶溶液,加入相应的培养板小孔中,随后将上述圆片织物称重并放入培养板小孔中,保证样品完全浸入酶溶液中。降解一定时间后,取出样品用大量的去离子水清洗,随后于37℃下真空烘干24h,并称重记录。
失重率计算公式如下:
其中W0为织物降解前的质量,Wi 为降解后的质量。
测得拒水织物降解72h后,质量残留率为30.3%。
实施例二
(1)生成N-苯基-N-叔丁氧羰基甘氨酸
2500mL单口烧瓶,配备磁力搅拌器。取40g N-苯基氨基乙酸于800mL的水/1,4-二氧六环的混合溶液(水和二氧六环的体积比为1:1)中溶解至完全透明,再用注射器加入184mL的三乙胺溶液,滴加含有142g Boc酸酐的400mL 1,4-二氧六环溶液,40min滴加完成。反应在室温下搅拌16h后,溶液用500mL正己烷萃取两次,再加入800mL的1 N HCl溶液使其呈酸性,再用2×300mL乙酸乙酯溶液萃取产物。合并有机相,用800mL的盐水洗涤有机层,去离子水水洗三次,无水硫酸镁干燥,过滤,减压蒸馏除去溶剂,得42.4g黑褐色粘稠状产物,产率64.3%。
(2)生成N-苯胺基酸酐
在氮气氛围下,将上述(1)所得产物溶于900mL的无水三氯甲烷溶液中,将溶液在低温反应釜中冷却至0℃,通过注射器将46.0g的PCl3溶液分三批(16g+15g+15g)加入到反应液中,间隔15min,反应液在0℃下搅拌1h,然后转移至室温下反应16小时。真空除去溶剂,将所得固体再溶于300mL的无水二氯甲烷,过滤,滤液蒸发后可得到约21.0g淡黄色粗产物固体,产率70%。将21.0g淡黄色固体在无水三氯甲烷/正己烷的混合溶液中进行重结晶,最后可得用于聚合的10.1g白色固体产物,产率47.6%。核磁图见图2,红外图见图3。
(3)织物的预处理:
将氨基硅烷偶联剂氨丙基三乙氧基硅烷溶于水/乙醇的混合溶液(水和乙醇的体积比为1:9)中,用10%的氨水调节溶液pH至10左右,在室温下水解3h得到氨基硅烷偶联剂透明水解液,然后将一块300g圆形麻织物于上述400mL氨基硅烷偶联剂水解液(氨基硅烷偶联剂用量为织物重量的6%)中,进行水浴反应,水浴温度50℃,反应时间为120min。反应完成后,取出织物,水洗三次,60℃烘干,120℃焙烘3min,得到预处理麻织物。
(4)制备拒水性麻织物:
取3.1g步骤(2)中的白色固体产物N-苯胺基酸酐于450mL的N,N-二甲基甲酰胺(DMF)溶液中完全溶解,将预处理后的织物加入到DMF的溶液中,在室温下反应4h,后升温至50℃反应8h,升温至60℃反应12h,最后升温至70℃反应12h,总接枝反应时间为48h。反应完成后,取出麻织物终止反应,水洗三次,常规超声波清洗15min,再60℃烘干,得到拒水性麻织物。测试织物表面红外光谱如图4,其中,3134.44cm-1为苯基取代基上C-H伸缩振动吸收峰,2935.56和2959.44cm-1处对应-CH2-吸收峰,1838.67和1780.79 cm-1为氨基酸C=O吸收峰,1958cm-1为苯环骨架特征吸收峰,红外测试说明苯基聚氨基酸接枝链已经在纤维表面形成。改性纤维表面接枝链结构如下(波浪线为纤维,n为50~90):
(5)皂洗牢度测试
处理布样按照GB/T 3921-2008《纺织品色牢度实验耐皂洗色牢度》进行皂洗后,测试接枝改性的皂洗耐久性。
(6)接触角测试
接触角测试采用德国Krüss公司的DSA100型全自动微观液滴润湿性测量仪对皂洗前后的涂层织物润湿性能测试,选取水作为测试液滴,液滴体积为5μL,分别测试五次取其平均值。测得皂洗前后酸酐开环聚合法整理织物表面接触角分别为141.2°和140.1°,皂洗后仍能表现出疏水性能,参见图5,表明整理耐久性好。
(7)降解性测试
拒水织物样品剪成直径大约10 mm的圆片,并依次以乙醇、去离子水清洗后,37℃下真空烘干24 h,备用。使用木瓜蛋白酶(Papain)作蛋白水解酶,蛋白酶在0.01M半胱氨酸,0.04M EDTA缓冲溶液中活化(pH8.0),浓度为lmg酶/ml溶液。使用移液管移取3mL酶溶液,加入相应的培养板小孔中,随后将上述圆片织物称重并放入培养板小孔中,保证样品完全浸入酶溶液中。降解一定时间后,取出样品用大量的去离子水清洗,随后于37℃下真空烘干24h,并称重记录。
失重率计算公式如下:
其中W0为织物降解前的质量,Wi 为降解后的质量。
测得拒水织物降解72h后,质量残留率为38.1%。
将步骤(4)的N-苯胺基酸酐更换为N-三氟甲苯胺基酸酐,其余不变,得到拒水性麻织物皂洗前后表面接触角分别为141.9°和139.3°。
实施例三
(1)根据实施例二步骤(3)制备经氨丙基三乙氧基硅烷预处理后的丝织物,将其中的麻织物更换为桑蚕丝织物,其余不变。
取0.25gN-苯胺基酸酐(实施例二制备),溶解于45mL的四氢呋喃(THF)中,将经氨丙基三乙氧基硅烷预处理后的丝织物加入到THF溶液中,在室温下反应2h,后升温至30℃反应4h,升温至50℃反应12h,升温至60℃反应12h,总接枝反应时间为24h。反应完成后,取出织物终止反应,水洗三次,常规超声波清洗15min,于60℃烘干,得到拒水丝织物。纤维表面聚氨基酸接枝链结构如下(波浪线为纤维,n为30~70):
(2)皂洗牢度测试
处理布样按照GB/T 3921-2008《纺织品色牢度实验耐皂洗色牢度》进行皂洗后,测试接枝改性丝织物的皂洗耐久性。
(3)接触角测试
接触角测试采用德国Krüss公司的DSA100型全自动微观液滴润湿性测量仪对皂洗前后的涂层织物润湿性能测试,选取水作为测试液滴,液滴体积为5μL,分别测试五次取其平均值。测得皂洗前后酸酐开环聚合法整理织物表面接触角分别为142.7°和139.8°,皂洗后仍能表现出疏水性能,参见图6,表明整理耐久性好。
(4)降解性测试
拒水织物样品剪成直径大约10 mm的圆片,并依次以乙醇、去离子水清洗后,37℃下真空烘干24 h,备用。使用木瓜蛋白酶(Papain)作蛋白水解酶,蛋白酶在0.01M半胱氨酸,0.04M EDTA缓冲溶液中活化(pH8.0),浓度为lmg酶/ml溶液。使用移液管移取3mL酶溶液,加入相应的培养板小孔中,随后将上述圆片织物称重并放入培养板小孔中,保证样品完全浸入酶溶液中。降解一定时间后,取出样品用大量的去离子水清洗,随后于37℃下真空烘干24h,并称重记录。
失重率计算公式如下:
其中W0为织物降解前的质量,Wi 为降解后的质量。
测得拒水丝织物降解72h后,质量残留率为22.8%,参见图7,为下行示意图。
对比例一
(1)制备拒水性丝织物:
取从3M公司购得的含氟拒水整理剂E-061,用去离子水开稀成质量浓度为30 g/L的整理液,将桑蚕丝织物用蒸馏水润湿后投入到整理液中(浴比1∶20),浸渍15 min。
整理工艺流程:二浸二扎(轧余率为80%)→预烘(90 ℃,3 min)→焙烘(155 ℃,2min)→整理丝织物。
(2)皂洗牢度测试
处理布样按照GB/T 3921-2008《纺织品色牢度实验耐皂洗色牢度》进行皂洗后,测试接枝改性丝织物的皂洗耐久性。
(3)接触角测试
接触角测试采用德国Krüss公司的DSA100型全自动微观液滴润湿性测量仪对皂洗前后的涂层织物润湿性能测试,选取水作为测试液滴,液滴体积为5μL,分别测试五次取其平均值。测得皂洗前后整理织物表面接触角分别为136.8°和108.1°,皂洗后接触角下降很多、疏水性能下降,整理耐久性欠佳。
(4)降解性测试
拒水织物样品剪成直径大约10 mm的圆片,并依次以乙醇、去离子水清洗后,37℃下真空烘干24 h,备用。使用木瓜蛋白酶(Papain)作蛋白水解酶,蛋白酶在0.01M半胱氨酸,0.04M EDTA缓冲溶液中活化(pH8.0),浓度为lmg酶/ml溶液。使用移液管移取3mL酶溶液,加入相应的培养板小孔中,随后将上述圆片织物称重并放入培养板小孔中,保证样品完全浸入酶溶液中。降解一定时间后,取出样品用大量的去离子水清洗,随后于37℃下真空烘干24h,并称重记录。
失重率计算公式如下:
其中W0为织物降解前的质量,Wi 为降解后的质量。
测得拒水丝织物降解72h后,质量残留率为98.1%,基本不降解,参见图7,为上行示意图。
未处理的桑蚕丝织物降解72h后,质量残留率为16.1%。
将上述桑蚕丝织物更换为经氨丙基三乙氧基硅烷预处理后的丝织物(实施例三),其余不变,得到的E-061处理丝织物皂洗前后整理织物表面水接触角分别为137.3°和106.5°,皂洗后接触角下降很多、疏水性能下降,整理耐久性欠佳。
对比例二
在实施例二的基础上,将在室温下反应4h,后升温至50℃反应8h,升温至60℃反应12h,最后升温至70℃反应12h,总接枝反应时间为48h更换为室温反应48h;其余不变,得到的拒水麻织物皂洗前后整理织物表面水接触角分别为134.7°和130.5°。
在实施例二的基础上,将在室温下反应4h,后升温至50℃反应8h,升温至60℃反应12h,最后升温至70℃反应12h,总接枝反应时间为48h更换为60℃反应48h;其余不变,得到的拒水麻织物皂洗前后整理织物表面水接触角分别为130.9°和122.3°。
本发明在预处理纤维表面引发诱导含苯胺基酸酐开环聚合形成接枝链,具有良好的拒水性能,尤其是耐水洗性以及可降解性优异。现有开环聚合法对材料表面进行接枝改性主要是关于硅基材料或者金属材料表面的接枝改性,鲜有文献报道关于在纤维表面利用开环聚合法获得改性和功能性的研究。本发明开环聚合由环状化合物单体经过开环反应转变成线型聚合物,反应条件较为温和;副反应比缩聚反应少,易于得到高分子量聚合物,开环聚合也不像加成反应时释放出那样多能量,其聚合过程的热效应是环张力的变化造成的,可以控制基底材料表面的化学组成并由此获得改性和功能性。
Claims (10)
2.根据权利要求1所述聚氨基酸接枝改性拒水织物,其特征在于,所述织物为棉织物、麻织物、毛织物、真丝织物中的一种或者几种;所述织物中纤维为棉、麻、毛、真丝等中的任意一种进行聚氨基酸接枝改性,改性纤维表面的聚氨基酸接枝链。
4.根据权利要求3所述聚氨基酸接枝改性拒水织物的制备方法,其特征在于,所述反应的温度为0~80℃,时间为1~120h;所述氨基预处理织物为氨基硅烷偶联剂处理的织物。
5.根据权利要求4所述聚氨基酸接枝改性拒水织物的制备方法,其特征在于,所述反应温度为四级阶梯升温。
7.根据权利要求6所述聚氨基酸接枝改性拒水织物的制备方法,其特征在于,在缚酸剂存在下,N-苯基氨基酸与Boc酸酐反应,得到N-苯基-叔丁氧碳基甘氨酸。
8.根据权利要求7所述聚氨基酸接枝改性拒水织物的制备方法,其特征在于,所述缚酸剂为三乙胺或吡啶;所述反应的温度为5~45℃,时间为0.1~24h。
9.权利要求1所述聚氨基酸接枝改性拒水织物在制备拒水材料中的应用。
10.根据权利要求9所述的应用,其特征在于,所述拒水材料具有耐洗性与降解性。
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