CN112898477A - 一种纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂的制备方法及应用 - Google Patents
一种纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂的制备方法及应用 Download PDFInfo
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- CN112898477A CN112898477A CN202110170754.1A CN202110170754A CN112898477A CN 112898477 A CN112898477 A CN 112898477A CN 202110170754 A CN202110170754 A CN 202110170754A CN 112898477 A CN112898477 A CN 112898477A
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Classifications
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
本发明公开了一种纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂的制备方法及应用,在无氟长链聚丙烯酸酯类防水剂制备过程中利用反应性季铵盐阳离子乳化剂和反应性非离子乳化剂协同乳化并参与聚合反应,将乳化剂分子同长链丙烯酸酯、短链烷基丙烯酸酯单体、交联型单体发生共聚键合到防水乳液高分子链中,同时利用有机硅试剂原位水解和硅烷偶联剂偶联作用在聚合物链中引入纳米SiO2粒子,从而开发出固含量高、粒径小且分布均一稳定且能赋予纺织品优良的防水性、耐久性及抗菌性的无皂无氟聚丙烯酸酯防水乳液。
Description
技术领域
本发明涉及纺织印染技术领域,特别是涉及一种纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂的制备方法及应用。
背景技术
随着经济的高度发展和人们生活的日益提高,“绿色、健康、低碳、环保”是人们所追求的生活目标。日常生活中跟人们息息相关的诸如野战军服、消防、军队特用服装、防护用品、军队用帐篷、睡袋、登山服、滑雪服、鞋帽用材、箱包、浴帘、休闲风衣、医护用品等无氟防水整理的纺织品越来越受到人们的欢迎,提高无氟防水剂的防水性和耐洗性,将是未来防水整理剂的发展趋势。纳米防水整理剂的纳米粒子容易发生凝聚,从而失去纳米特性,而且粒子凝聚特别容易发生粘辊现象,导致织物的防水性大大降低。长碳链丙烯酸酯类高聚物具有较好的耐水性、耐溶剂性、成膜性以及附着力强、生产工艺简单、成本低廉等优点,利用其制备的乳液型无氟聚丙烯酸酯类防水剂以水为连续相,具有成本低、安全无毒、环保等优点,但该类防水剂乳液的粒径及其分布范围对乳液的稳定性影响巨大,乳液粒径过大,会产生凝胶现象,影响其使用性能,此外,该类防水剂乳液制备过程中所用的乳化剂分子结构也将对后续其防水膜的耐久性产生关键影响。
ZL201910777219.5将长碳链丙烯酸酯和其他功能单体的体系中引入阳离子单体,以阳离子乳化剂和非离子乳化剂组成的复合乳化体系利用微乳液聚合的方法制备无氟阳离子聚丙烯酸酯防水剂,该防水剂在防水乳液中引入阳离子,较好地改善了防水剂乳液的粒径,防止了乳液凝胶现象的产生,较好地提高了乳液的稳定性,但该防水乳液体系中因为使用了小分子的乳化剂,这类小分子乳化剂在后续使用过程中会析出,使防水膜层发生松弛,影响到防水剂的耐久性。ZL201910903695.7将长碳链丙烯酸酯和其他功能单体的体系中引入长链阳离子单体参与聚合反应,反应体系中以长链阳离子单体作为乳化剂利用微乳液聚合的方法制备无氟阳离子聚丙烯酸酯防水剂,该类防水剂虽然将乳化剂以反应单体的形式共聚到防水剂高分子链段中,使制备的防水剂在后续使用过程中防水剂膜层无小分子乳化剂析出,但该反应体系中仅仅使用阳离子单体做乳化剂,乳化效果不够理想,会使制备的防水剂乳液粒径较大而稳定性差,另外仅仅靠防水剂乳液在织物表面引入疏水层的方法提高防水效果,其防水效果有限。
ZL201810932016.4利用长链烷基丙烯酸酯同短链烷基丙烯酸酯乳液共聚制备防水剂乳液的过程中,引入硅烷偶联剂改性的SiO2纳米粒子和大粒径粒子到聚合物体系制备核壳型无氟聚丙烯酸酯防水剂,但现成的SiO2纳米粒子分散性不好,虽然利用硅烷偶联剂进行修饰,仍然克服不了纳米粒子团聚颗粒大的问题,大粒径粒子直接加入到聚合物反应体系中,也存在分散性不好的问题,从而使聚合物乳液粒子会较大,防水乳液容易团聚产生凝胶现象,影响了其性能的发挥。
发明内容
本发明的目的在于克服上述现有技术的不足,提供一种纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂的制备方法及应用,利用反应性季铵盐阳离子乳化剂和反应性非离子乳化剂协同乳化并参与聚合反应的作用,将乳化剂分子键合到防水剂高分子链中,同时利用原位水解和共聚法在聚合物链中引入纳米SiO2粒子,使开发出的防水剂乳液具有固含量高、粒径小且分布均一稳定的特点,从而赋予纺织品优良的拒水性、耐久性及抗菌性等性能。
为了实现上述目的,本发明采用如下技术方案:
一种纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂的制备方法,包括以下步骤:
(a)按质量百分比称取原料:无氟疏水性长链烷基丙烯酸酯单体15-28.5%、短链烷基丙烯酸酯单体1-10%、可交联单体0.3-5%、反应性阳离子乳化剂0.5-5%、反应性非离子乳化剂0.5-5%,余量为去离子水,其中无氟疏水性长链烷基丙烯酸酯单体、短链烷基丙烯酸酯单体、可交联单体组成混合单体;将无氟疏水性长链烷基丙烯酸酯单体、短链烷基丙烯酸酯单体、可交联单体、反应性阳离子乳化剂、反应性非离子乳化剂和去离子水在40-55℃搅拌溶解,其后在超声波下高速搅拌,形成带有蓝光的单体预乳液;
(b)将1/3份单体预乳液加入反应釜中,通氮气30min,然后加入1/3份引发剂水溶液,升温至80-90℃,反应20-50min,再在40-120min内滴加剩余的2/3份单体预乳液和引发剂水溶液;
(c)滴加完毕后,向反应体系中加入占混合单体和乳化剂总质量1-15%的硅烷偶联剂,在80-90℃反应90-180min,然后降温至50℃,再加入占混合单体和乳化剂总质量2-15%的正硅酸乙酯,反应8-15h,反应结束后降至室温,出料,即制得纳米二氧化硅改性无氟阳离子聚丙烯酸酯防水剂。
所述无氟疏水性长链烷基丙烯酸酯单体选自10至24个碳原子的醇的丙烯酸酯或10至24个碳原子的醇的甲基丙烯酸酯,或上述丙烯酸酯和甲基丙烯酸酯的混合物。
所述含有10至24个碳原子的醇的丙烯酸酯或含有10至24个碳原子的醇的甲基丙烯酸酯是支链的、直链的或环状的。
所述短链烷基丙烯酸酯单体选自甲基丙烯酸甲酯、丙烯酸甲酯、甲基丙烯酸异冰片酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸正丁酯、丙烯酸仲丁酯、丙烯酸异丁酯、丙烯酸-2-乙基己酯、甲基丙烯酸正辛酯中的一种或多种。
所述可交联单体选自丙烯酰胺、甲基丙烯酰胺、甲基丙烯酸羟乙酯、N-羟甲基丙烯酰胺、甲基丙烯酸羟丙酯、甲基丙烯酸缩水甘油酯、丙烯酸羟乙酯、丙烯酸缩水甘油酯、丙烯酸羟丙酯、3-氯-2-羟基丙基丙烯酸酯、3-氯-2-羟基丙基甲基丙烯酸酯中的一种或多种。
所述反应性阳离子乳化剂为丙烯酰氧烷基季铵盐类阳离子乳化剂中的一种或多种,其结构为:
其中,R1=H-、CH3-;R2=-CH3、-CH2CH3;R3=十二烷基、十四烷基、十六烷基、十八烷基、二十二烷基碳链或苄基。
所述反应性非离子乳化剂为聚乙二醇单烯丙基醚、1-烯丙氧基-3-(4-壬基苯酚)-2-丙醇聚氧乙烯(10)醚、壬基酚聚氧乙烯(4)醚丙烯酸酯中的一种或多种。
所述硅烷偶联剂为含双键的烷氧基硅烷中的一种或多种,包括γ-甲基丙烯酰氧丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三(β-甲氧基乙氧基)硅烷。
所述引发剂选自过硫酸盐、油溶性偶氮类引发剂、水溶性偶氮类引发剂中的一种或多种,引发剂添加量占混合单体和乳化剂总质量的0.4-1.2%。
所述纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂可应用于纺织品的防水整理。
本发明的有益效果是:
(1)以反应性季铵盐长链阳离子乳化剂和反应性非离子乳化剂作为乳化剂的同时也作为反应物质参与聚丙烯酸酯的共聚反应,利用两者的协同乳化作用有效防止凝胶现象的发生,从而促进聚合反应的进行并有利于控制聚合物粒径,有效提高了防水剂乳液的分散性和稳定性,通过将反应性季铵盐长链阳离子乳化剂和反应性非离子乳化剂分子键合到防水剂共聚物分子链上,解决了防水剂在织物防水整理应用中的小分子乳化剂析出问题,从而保证了所生成的防水剂膜层的长久致密性,大幅提高了防水剂膜层的使用耐久性。
(2)在反应体系中将有机硅试剂利用原位水解的方法制备SiO2纳米粒子,并利用硅烷偶联剂的烷氧基水解生成物与SiO2纳米粒子表面的-OH发生键合,从而得到纳米SiO2改性无皂无氟阳离子聚丙烯酸酯防水剂。由于引入的SiO2纳米粒子是原位水解法制备并键合到防水剂聚合物链上,使得防水剂粒径容易控制为所需的纳米级微小颗粒,并具有良好的分散性,同时也能在织物防水整理应用中生成更加致密的防水剂膜,进一步提高耐久性;引入的纳米SiO2具有纳米尺寸效应和大比表面积,赋予了防水剂膜优异的表面性能、力学性能和热学性能,且能使膜层具有类似荷叶表面的微/纳米乳突结构,从而使被处理织物呈现超强的疏水性能。
本发明制备方法简单易操作,反应条件温和,开发出的防水剂乳液具有固含量高、粒径小且分布均一稳定的特点,并能赋予纺织品优良的拒水性、耐久性及抗菌性,适合工业化生产。
附图说明
图1为本发明的实施例1制备的纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂涂膜的接触角测定示意图;
图2为本发明的实施例1制备的纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂的TEM图;
图3为本发明的实施例1制备的纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂的粒径分布图;
图4为本发明的实施例1制备的纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂放置12个月后的外观图。
具体实施方式
下面结合附图和具体实施方式对本发明作进一步描述:
实施例1
取16g甲基丙烯酸山嵛基酯,0.4g甲基丙烯酸甲酯,0.6g丙烯酸正丁酯,0.5g甲基丙烯酰氧乙基二甲基十八烷基氯化铵,0.4g甲基丙烯酸缩水甘油酯,2.1g1-烯丙氧基-3-(4-壬基苯酚)-2-丙醇聚氧乙烯(10)醚,80g水。将混合单体、乳化剂、去离子水加入烧杯,在40℃下搅拌溶解,其后在超声波下高速搅拌,形成带有蓝光的单体预乳液。取0.08g偶氮二异丁腈配制成水溶液。将1/3份单体预乳液加在装有搅拌器、温度计及加料装的反应釜中通入氮气30min,加入1/3份偶氮二异丁腈水溶液,并升温至所需80℃,反应20min,再在40min内滴加剩余的2/3份单体预乳液和引发剂水溶液;滴加完毕后,加入0.2g的乙烯基三乙氧基硅烷,在80℃反应90min,然后降温至50℃,再加入0.4g正硅酸乙酯反应8h,温度降至室温,出料,即制得纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂。
实施例1制备的纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂的分析测试数据:
(1)合成的纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯乳液涂膜接触角分析
将合成的阳离子聚丙烯酸酯防水剂乳液对棉纤维进行处理,然后烘干再焙烘,采用悬滴法测定接触角,结果如图1所示,测试结果显示,乳胶膜的水接触角为151°,表面张力较小,非润湿效果非常好。
(2)形貌分析
乳胶粒的形貌用TEM进行表征,如图2(图b为图a的部分放大图)。在乳液聚合中,乳液粒径平均的大小和分布是检验乳液稳定性能的一个重要指标,乳液粒径越小,分布越均匀所制备的乳液稳定性越高。由图2可以看出,乳胶粒外观基本呈球状,大小较为均匀。由图3可知实验所得乳液的粒径分布在100-300nm,平均粒径为218nm,分布较窄,而此结果基本与TEM估算粒径大小相一致。
(3)稳定性分析
将防水剂放置12个月后再次测试其平均粒径为232nm,粒径略有增加,分布稍增宽,由图4可知乳液外观并没有大的颗粒和挂壁现象,因此,制备的防水剂具有稳定储存性能。
实施例2
取20g甲基丙烯酸十八烷基酯,1.4g甲基丙烯酸异冰片酯,1.8g丙烯酸甲酯,3.8g甲基丙烯酰氧乙基二甲基二十二烷基氯化铵,1.2g甲基丙烯酸羟乙酯,1.5g聚乙二醇单烯丙基醚,70.3g水。将混合单体、乳化剂、去离子水加入烧杯,在50℃下搅拌溶解,其后在超声波下高速搅拌,形成带有蓝光的单体预乳液。取0.25g过硫酸铵配制成水溶液。将1/3份单体预乳液加在装有搅拌器、温度计及加料装的反应釜中通入氮气30min,加入1/3份过硫酸铵水溶液,并升温至所需85℃,反应30min,再在60min内滴加剩余的2/3份单体预乳液和引发剂水溶液;滴加完毕后,加入1.26g的乙烯基三甲氧基硅烷,在85℃反应100min,然后降温至50℃,再加入1.26g正硅酸乙酯反应12h,温度降至室温,出料,即制得纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂。
实施例3
取22.95g丙烯酸十八烷基酯,6.5g甲基丙烯酸正丁酯,2.5g丙烯酸乙酯,1.8g丙烯酰氧乙基二乙基十六烷基氯化铵,1.25g的3-氯-2-羟基丙基丙烯酸酯,3.3g壬基酚聚氧乙烯(4)醚丙烯酸酯,61.7g水。将混合单体、乳化剂、去离子水加入烧杯,在55℃下搅拌溶解,其后在超声波下高速搅拌,形成带有蓝光的单体预乳液。取0.36g偶氮二异丁眯盐酸盐配制成水溶液。将1/3份单体预乳液加在装有搅拌器、温度计及加料装的反应釜中通入氮气30min,加入1/3份的偶氮二异丁眯盐酸盐水溶液,并升温至所需90℃,反应40min,再在120min内滴加剩余的2/3份单体预乳液和引发剂水溶液;单体滴加完毕后,加入3.6g的γ-甲基丙烯酰氧丙基三甲氧基硅烷,在90℃反应120min,然后降温至50℃,再加入4.75g正硅酸乙酯反应15h,温度降至室温,出料,即制得纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂。
实施例4
取25g甲基丙烯酸山嵛基酯,1.8g甲基丙烯酸乙酯,1.8g丙烯酸正丙酯,5g甲基丙烯酰氧乙基二乙基十八烷基氯化铵,1.5g丙烯酸羟丙酯,3g辛基酚聚氧乙烯醚丙烯酸酯,61.9g水。将混合单体、乳化剂、去离子水加入烧杯,在55℃下搅拌溶解,其后在超声波下高速搅拌,形成带有蓝光的单体预乳液。取0.42g偶氮二异丁眯盐酸盐制成水溶液。将1/3份单体预乳液加在装有搅拌器、温度计及加料装的反应釜中通入氮气30min,加入1/3份的偶氮二异丁眯盐酸盐水溶液,并升温至所需85℃,反应50min,再在120min内滴加剩余的2/3份单体预乳液和引发剂水溶液;单体滴加完毕后,加入5.2g乙烯基三甲氧基硅烷,在90℃反应180min,然后降温至50℃,再加入3.5g正硅酸乙酯反应15h,温度降至室温,出料,即制得纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂。
实施例5
取25g甲基丙烯酸十八烷基酯,2g甲基丙烯酸正辛酯,1g丙烯酸仲丁酯,1.2g甲基丙烯酰氧乙基二甲基十四烷基氯化铵,5g丙烯酸缩水甘油酯,4g壬基酚聚氧乙烯(4)醚丙烯酸酯,61.8g水。将混合单体、乳化剂、去离子水加入烧杯,在50℃下搅拌溶解,其后在超声波下高速搅拌,形成带有蓝光的单体预乳液。取0.36g偶氮二异丁腈制成水溶液。将1/3份单体预乳液加在装有搅拌器、温度计及加料装的反应釜中通入氮气30min,加入1/3份的偶氮二异丁腈水溶液,并升温至所需90℃,反应50min,再在90min内滴加剩余的2/3份单体预乳液和引发剂水溶液;单体滴加完毕后,加入5g的乙烯基三乙氧基硅烷,在90℃反应180min,然后降温至50℃,再加入3.6g正硅酸乙酯反应12h,温度降至室温,出料,即制得纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂。
实施例6
取27.1g丙烯酸山嵛基酯,1.4g丙烯酸十八烷基酯,1.4g丙烯酸异丁酯,5g丙烯酰氧乙基二甲基十二烷基氯化铵,0.3g丙烯酸羟乙酯,0.5g1-烯丙氧基-3-(4-壬基苯酚)-2-丙醇聚氧乙烯(10)醚,64.3g水。将混合单体、乳化剂、去离子水加入烧杯,在55℃下搅拌溶解,其后在超声波下高速搅拌,形成带有蓝光的单体预乳液。取0.32g偶氮二异丁腈制成水溶液。将1/3份单体预乳液加在装有搅拌器、温度计及加料装的反应釜中通入氮气30min,加入1/3份的偶氮二异丁腈水溶液,并升温至所需90℃,反应50min,再在120min内滴加剩余的2/3份单体预乳液和引发剂水溶液;单体滴加完毕后,加入3.21g的乙烯基三甲氧基硅烷,在85℃反应150min,然后降温至50℃,再加入4g正硅酸乙酯反应12h,温度降至室温,出料,即制得纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂。
实施例7
取23g甲基丙烯酸二十四烷基酯,0.3g甲基丙烯酸癸酯,2g甲基丙烯酸甲酯,2g甲基丙烯酰氧乙基二乙基十六烷基氯化铵,2g甲基丙烯酰氧乙基二甲基十八烷基氯化铵,0.5g丙烯酰胺,1g甲基丙烯酸羟乙酯,2g聚乙二醇单烯丙基醚,1.5g1-烯丙氧基-3-(4-壬基苯酚)-2-丙醇聚氧乙烯(10)醚,65.7g水。将混合单体、乳化剂、去离子水加入烧杯,在40℃下搅拌溶解,其后在超声波下高速搅拌,形成带有蓝光的单体预乳液。取0.07g偶氮二异丁腈和0.14g过硫酸铵配制成引发剂水溶液。将1/3份单体预乳液加在装有搅拌器、温度计及加料装的反应釜中通入氮气30min,加入1/3份引发剂水溶液,并升温至所需80℃,反应20min,再在40min内滴加剩余的2/3份单体预乳液和引发剂水溶液;滴加完毕后,加入1.8g乙烯基三乙氧基硅烷和1.5g的γ-甲基丙烯酰氧丙基三甲氧基硅烷,在80℃反应90min,然后降温至50℃,再加入3.12g正硅酸乙酯反应8h,温度降至室温,出料,即制得纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂。
实施例8
取15g甲基丙烯酸山嵛基酯,11g丙烯酸十四烷基酯,1g甲基丙烯酸正丁酯,1g丙烯酸乙酯,0.5g丙烯酸仲丁酯,0.4g丙烯酰氧乙基二甲基十四烷基氯化铵,0.8g甲基丙烯酰氧乙基二甲基二十二烷基氯化铵,0.3g甲基丙烯酰胺,0.2g的3-氯-2-羟基丙基丙烯酸酯,0.5g壬基酚聚氧乙烯(4)醚丙烯酸酯,0.5g辛基酚聚氧乙烯醚丙烯酸酯,68.8g水。将混合单体、乳化剂、去离子水加入烧杯,在50℃下搅拌溶解,其后在超声波下高速搅拌,形成带有蓝光的单体预乳液。取0.1g偶氮二异丁眯盐酸盐和0.05g偶氮二异丁腈配制成引发剂水溶液。将1/3份单体预乳液加在装有搅拌器、温度计及加料装的反应釜中通入氮气30min,加入1/3份过引发剂水溶液,并升温至所需85℃,反应30min,再在60min内滴加剩余的2/3份单体预乳液和引发剂水溶液;滴加完毕后,加入1.25g乙烯基三甲氧基硅烷和2.4g的γ-甲基丙烯酰氧丙基三甲氧基硅烷,在85℃反应100min,然后降温至50℃,再加入2.92g的正硅酸乙酯反应12h,温度降至室温,出料,即制得纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂。
实施例9
取10g甲基丙烯酸异癸酯,8.2g丙烯酸十八烷基酯,3.6g丙烯酸-2-乙基己酯,1g甲基丙烯酰氧乙基二乙基十八烷基氯化铵,0.8g丙烯酰氧乙基二乙基十六烷基氯化铵,0.5g的N-羟甲基丙烯酰胺,0.5g甲基丙烯酸羟丙酯,0.5g的3-氯-2-羟基丙基丙烯酸酯,2.5g聚乙二醇单烯丙基醚,0.5g壬基酚聚氧乙烯(4)醚丙烯酸酯,71.9g水。将混合单体、乳化剂、去离子水加入烧杯,在55℃下搅拌溶解,其后在超声波下高速搅拌,形成带有蓝光的单体预乳液。取0.129g过硫酸铵和0.129g偶氮二异丁眯盐酸盐配制成引发剂水溶液。将1/3份单体预乳液加在装有搅拌器、温度计及加料装的反应釜中通入氮气30min,加入1/3份的引发剂水溶液,并升温至所需90℃,反应40min,再在120min内滴加剩余的2/3份单体预乳液和引发剂水溶液;单体滴加完毕后,加入0.23g的γ-甲基丙烯酰氧丙基三甲氧基硅烷、0.5g乙烯基三(β-甲氧基乙氧基)硅烷和0.5g乙烯基三乙氧基硅烷,在90℃反应120min,然后降温至50℃,再加入1.66g正硅酸乙酯反应15h,温度降至室温,出料,即制得纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂。
实施例10
取7g丙烯酸十四烷基酯,18.5g甲基丙烯酸癸酯,1.3g丙烯酸正丙酯,2.5g甲基丙烯酸正辛酯,2g丙烯酸异丁酯,1.6g丙烯酰氧乙基二乙基二十二烷基氯化铵,2g的3-氯-2-羟基丙基甲基丙烯酸酯,0.5g丙烯酸羟丙酯,2.1g丙烯酸羟乙酯,3g聚乙二醇单烯丙基醚,2g辛基酚聚氧乙烯醚丙烯酸酯,57.5g水。将混合单体、乳化剂、去离子水加入烧杯,在55℃下搅拌溶解,其后在超声波下高速搅拌,形成带有蓝光的单体预乳液。取0.13g偶氮二异丁腈、0.13g过硫酸铵和0.13g偶氮二异丁眯盐酸盐制成引发剂水溶液。将1/3份单体预乳液加在装有搅拌器、温度计及加料装的反应釜中通入氮气30min,加入1/3份引发剂水溶液,并升温至所需85℃,反应50min,再在120min内滴加剩余的2/3份单体预乳液和引发剂水溶液;单体滴加完毕后,加入2g的γ-甲基丙烯酰氧丙基三甲氧基硅烷和3g乙烯基三(β-甲氧基乙氧基)硅烷,在90℃反应180min,然后降温至50℃,再加入5.6g正硅酸乙酯反应15h,温度降至室温,出料,即制得纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂。
实施例11
取18g甲基丙烯酸山嵛基酯,9.6g甲基丙烯酸月桂酯,10g甲基丙烯酸异冰片酯,4g丙烯酰氧乙基二甲基十八烷基氯化铵,3.6g的N-羟甲基丙烯酰胺,3.3g聚乙二醇单烯丙基醚,51.5g水。将混合单体、乳化剂、去离子水加入烧杯,在50℃下搅拌溶解,其后在超声波下高速搅拌,形成带有蓝光的单体预乳液。取0.1g偶氮二异丁腈、0.2g过硫酸铵和0.1g偶氮二异丁眯盐酸盐制成水溶液。将1/3份单体预乳液加在装有搅拌器、温度计及加料装的反应釜中通入氮气30min,加入1/3份的偶氮二异丁腈水溶液,并升温至所需90℃,反应50min,再在90min内滴加剩余的2/3份单体预乳液和引发剂水溶液;单体滴加完毕后,加入3.2g乙烯基三(β-甲氧基乙氧基)硅烷、0.6g乙烯基三乙氧基硅烷和1g乙烯基三甲氧基硅烷,在90℃反应180min,然后降温至50℃,再加入4.8g的正硅酸乙酯反应12h,温度降至室温,出料,即制得纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂。
实施例12
取15g甲基丙烯酸月桂酯,1.2g丙烯酸乙酯,0.2g甲基丙烯酰氧乙基二甲基苄基氯化铵,0.4g甲基丙烯酰氧乙基二甲基十八烷基氯化铵,0.2g丙烯酰氧丙基二甲基十八烷基氯化铵,0.5g甲基丙烯酰胺,1.5g壬基酚聚氧乙烯(4)醚丙烯酸酯,1g辛基酚聚氧乙烯醚丙烯酸酯,80g水。将混合单体、乳化剂、去离子水加入烧杯,在55℃下搅拌溶解,其后在超声波下高速搅拌,形成带有蓝光的单体预乳液。取0.24g偶氮二异丁眯盐酸盐制成水溶液。将1/3份单体预乳液加在装有搅拌器、温度计及加料装的反应釜中通入氮气30min,加入1/3份的偶氮二异丁眯盐酸水溶液,并升温至所需90℃,反应50min,再在120min内滴加剩余的2/3份单体预乳液和引发剂水溶液;单体滴加完毕后,加入3g乙烯基三甲氧基硅烷,在85℃反应150min,然后降温至50℃,再加入3g正硅酸乙酯反应12h,温度降至室温,出料,即制得纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂。
对比实施例1-12
按照实施例1-12所述方法制备防水剂,不同之处在于使用短链季铵盐阳离子单体和非反应性阳离子乳化剂替代反应性阳离子乳化剂(短链季铵盐阳离子单体和非反应性阳离子乳化剂的摩尔比为1:1),使用非反应性非离子乳化剂替代反应性非离子乳化剂,并在加入硅烷偶联剂反应后,不再添加硅酸乙酯,得到未经纳米二氧化硅改性的阳离子聚丙烯酸酯乳液。
对比实施例13
无皂无氟防水剂是市售商品。
本发明还提供纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂在纺织品防水整理上的应用。
应用步骤包括先将以本发明提供的方法制备的无皂无氟防水剂稀释至0.1-10%质量分数,然后施加到经低温染整加工的棉织物上接着去除多余的液体,最后进行干燥处理。可以通过涂布、喷涂、辊涂、轧染、浸渍等方法以及这些方法的组合,将无皂无氟防水剂施加到经低温染整加工的棉织物上。经检测,附着在经低温染整加工的棉织物上的无皂无氟防水剂成分占经低温染整加工的棉织物的质量比例为0.01-10%。所述干燥焙烘处理中,干燥条件依经低温染整加工的棉织物种类的不同而有所差异,同时应该保证无氟防水剂中由功能单体带来的功能基团充分反应,以达到最佳的防水效果和耐久性,通常需要在先在100℃-200℃下处理0.1-90min。
将实施例1-12和对比实施例1-13的防水剂用自来水稀释到固含量为10%,取经低温染整加工的棉织物一浸一轧,100℃烘干,165℃热处理60s,冷却到室温后测定防水效果。
防水性能:按照AATCC 22-2017《拒水性/淋雨泼水测试》在织物喷淋测试仪上进行测试,并采用标准比样卡评分。
耐水洗性能:根据GB/T 8629-2017《纺织品试验用家庭洗涤和干燥程序》对织物进行水洗,参照AATCC 22-2017进行防水性能测试。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员,在不脱离本发明构思的前提下,还可以做出若干改变、改进和润饰,这些改变、改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂的制备方法,其特征在于:包括以下步骤:
(a)按质量百分比称取原料:无氟疏水性长链烷基丙烯酸酯单体15-28.5%、短链烷基丙烯酸酯单体1-10%、可交联单体0.3-5%、反应性阳离子乳化剂0.5-5%、反应性非离子乳化剂0.5-5%,余量为去离子水,其中无氟疏水性长链烷基丙烯酸酯单体、短链烷基丙烯酸酯单体、可交联单体组成混合单体;将无氟疏水性长链烷基丙烯酸酯单体、短链烷基丙烯酸酯单体、可交联单体、反应性阳离子乳化剂、反应性非离子乳化剂和去离子水在40-55℃搅拌溶解,其后在超声波下高速搅拌,形成带有蓝光的单体预乳液;
(b)将1/3份单体预乳液加入反应釜中,通氮气30min,然后加入1/3份引发剂水溶液,升温至80-90℃,反应20-50min,再在40-120min内滴加剩余的2/3份单体预乳液和引发剂水溶液;
(c)滴加完毕后,向反应体系中加入占混合单体和乳化剂总质量1-15%的硅烷偶联剂,在80-90℃反应90-180min,然后降温至50℃,再加入占混合单体和乳化剂总质量2-15%的正硅酸乙酯,反应8-15h,反应结束后降至室温,出料,即制得纳米二氧化硅改性无氟阳离子聚丙烯酸酯防水剂。
2.如权利要求1所述一种纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂的制备方法,其特征在于:所述无氟疏水性长链烷基丙烯酸酯单体选自10至24个碳原子的醇的丙烯酸酯或10至24个碳原子的醇的甲基丙烯酸酯,或上述丙烯酸酯和甲基丙烯酸酯的混合物。
3.如权利要求2所述一种纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂的制备方法,其特征在于:所述含有10至24个碳原子的醇的丙烯酸酯或含有10至24个碳原子的醇的甲基丙烯酸酯是支链的、直链的或环状的。
4.如权利要求1所述一种纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂的制备方法,其特征在于:所述短链烷基丙烯酸酯单体选自甲基丙烯酸甲酯、丙烯酸甲酯、甲基丙烯酸异冰片酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸正丁酯、丙烯酸仲丁酯、丙烯酸异丁酯、丙烯酸-2-乙基己酯、甲基丙烯酸正辛酯中的一种或多种。
5.如权利要求1所述一种纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂的制备方法,其特征在于:所述可交联单体选自丙烯酰胺、甲基丙烯酰胺、甲基丙烯酸羟乙酯、N-羟甲基丙烯酰胺、甲基丙烯酸羟丙酯、甲基丙烯酸缩水甘油酯、丙烯酸羟乙酯、丙烯酸缩水甘油酯、丙烯酸羟丙酯、3-氯-2-羟基丙基丙烯酸酯、3-氯-2-羟基丙基甲基丙烯酸酯中的一种或多种。
7.如权利要求1所述一种纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂的制备方法,其特征在于:所述反应性非离子乳化剂为聚乙二醇单烯丙基醚、1-烯丙氧基-3-(4-壬基苯酚)-2-丙醇聚氧乙烯(10)醚、壬基酚聚氧乙烯(4)醚丙烯酸酯中的一种或多种。
8.如权利要求1所述一种纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂的制备方法,其特征在于:所述硅烷偶联剂为含双键的烷氧基硅烷中的一种或多种,包括γ-甲基丙烯酰氧丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三(β-甲氧基乙氧基)硅烷。
9.如权利要求1所述一种纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂的制备方法,其特征在于:所述引发剂选自过硫酸盐、油溶性偶氮类引发剂、水溶性偶氮类引发剂中的一种或多种,引发剂添加量占混合单体和乳化剂总质量的0.4-1.2%。
10.一种如权利要求1-9中任意一项所述制备方法制备的纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂的应用,其特征在于:所述纳米二氧化硅改性无皂无氟阳离子聚丙烯酸酯防水剂可应用于纺织品的防水整理。
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