CN117552238A - 一种生物基无氟防水剂及其制备方法和应用 - Google Patents
一种生物基无氟防水剂及其制备方法和应用 Download PDFInfo
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- CN117552238A CN117552238A CN202311456375.4A CN202311456375A CN117552238A CN 117552238 A CN117552238 A CN 117552238A CN 202311456375 A CN202311456375 A CN 202311456375A CN 117552238 A CN117552238 A CN 117552238A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
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- D—TEXTILES; PAPER
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
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- D—TEXTILES; PAPER
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/17—Natural resins, resinous alcohols, resinous acids, or derivatives thereof
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- D—TEXTILES; PAPER
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
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- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
本发明属于纺织工业印染生产中纺织品印染技术领域,尤其是涉及一种生物基无氟防水剂及其制备方法和应用。首先,在反应中加入生物基单体,其次,引入松香基氨基酸表面活性剂,这是一种生物基的两性表面活性剂,具有污性好、耐硬水、对酸碱稳定,并具有杀菌、防腐、抗静电等性能;最后,在反应后加入木质素‑糠醛生物基树脂,这是一种新型糠醛类的生物基树脂,树脂会均匀地交联在纱线表层,使纤维末梢粘附于纱线上,而且树脂较强的粘合力可以对纤维进行粘结,以限制其移动。本发明制成的无氟防水剂原料来源于生物基产品,在自然环境中可以完全生物降解,环保安全,提升了产品的可再生及环境友好价值,具有显著的社会效益和广阔的市场前景。
Description
技术领域
本发明属于纺织工业印染生产中纺织品印染技术领域,尤其是涉及一种生物基无氟防水剂及其制备方法和应用。
背景技术
随着生活质量和消费水平的不断提高,人们对服装的穿着舒适度和特种功能的要求越来越高,以及登高、滑雪、冲浪、骑行、露营等户外运动在国内外的流行,防水整理的应用越来越广泛,而且要求越来越高,特别是户外运动装备。登山时,完整的装备至少包括冲锋衣、帐篷、保温服、防水鞋、防水雨衣等,这些装备都是做过防水整理的。
所谓防水就是指织物经过特殊处理后,水滴会落到织物上,形成圆珠并滑落。水滴不会扩散甚至渗透到织物上,从而弄湿织物。
织品在加工或日常使用中,经多次加工、洗涤处理后手感会变得粗糙,一般合成纤维织物手感更差。为了使织物具有柔软、凉爽、顺滑、舒适的手感,和防水功能,就需要对其进行整理,目前应用广泛的是用防水剂进行整理。因此后整理是纺织印染加工中提高产品质量,增加产品附加价值必不可少的一种重要工序。
防水剂的种类很多,主要是吡啶季铵盐类、羟甲基三聚氰胺衍生物类、有机硅类防水剂等防水效果好但是手感一般;氟碳类防水防油剂纺效果好,手感好,耐洗涤,但是全氟碳化合物中含有PFOA、PFOS和APEO,这些目前在环境中很难被降解,有生物累积性和多种毒性,具备持久性有机污染物的共同特性,被认为是21世纪重点研究的新型持久性环境污染物,不符合纺织品工业的发展趋势和要求。
目前常见的防水剂,在生产车间加工时气味大,对工作环境和操作者不友好;水洗后防水效果下降,影响将来纺织品的使用效果。
发明内容
本发明的目的在于提供一种生物基无氟防水剂及其制备方法和应用,本发明提供的无氟防水剂稳定性好、无气味,织物处理后色变小、绑纱牢度好、手感有韧性、无折痕。同时该无氟防水剂来源天然,可降解对环境无污染,整理后的织物可直接接触人体,无细胞毒性,对皮肤无刺激,适合广泛应用。
为达此目的,本发明采用以下技术方案:
一种生物基无氟防水剂,该无氟防水剂的原料包括生物基单体、基体单体、功能性单体、引发剂、生物基乳化剂、天然油脂磺化油、松香基氨基酸表面活性剂、木质素-糠醛生物基树脂、pH调节剂、消泡剂和去离子水;
以该无氟防水剂的原料的总质量为100%计算,各组份的质量百分含量为:
生物基单体 15%-25%
基体单体 2%-5%
功能性单体 1%-3%
引发剂 0.01%-0.4%
生物基乳化剂 1%-5%
天然油脂磺化油 1%-5%
松香基氨基酸表面活性剂 1%-5%
木质素-糠醛生物基树脂 5%-15%
pH调节剂 0.01%-1%
消泡剂 0.01%-0.5%
余量为去离子水。
其中,所述的生物基单体为生物基甲基丙烯酸十八烷基酯、生物基丙烯酸十八烷基酯中的至少一种;
所述的单体为甲基丙烯酸丁酯、甲基丙烯酸甲酯、烷基烯酮二聚体、丙烯酸十二烷基酯中的至少一种;
所述的功能性单体为甲基丙烯酰胺、甲基丙烯酸羟乙酯、甲基丙烯酰吗啉、丙烯酸羟乙酯中的至少一种;
所述的引发剂为偶氮二异丁脒盐酸盐、过硫酸铵、过硫酸钾中的至少一种;
所述的生物基乳化剂为腰果酚聚氧乙烯醚NSS1305、NSS1305A、NSS 1308、十八烷基三甲基溴化铵中的至少一种;
所述的天然油脂磺化油为天然磺化菜籽油、天然磺化蓖麻油、硫酸化天然牛蹄油中的至少一种;
所述pH调节剂为氨水、液碱、碳酸钠中至少一种;
所述的消泡剂为聚氧丙基聚氧乙基甘油醚、聚醚改性聚硅氧烷类中的至少一种。
一种生物基无氟防水剂的制备方法,其中包括以下步骤:
一种生物基无氟防水剂的制备方法,步骤包括:
步骤一、将去离子水质量的20%-30%、生物基乳化剂质量的55%-70%、天然油脂磺化油质量的55%-65%、生物基单体、基体单体、功能性单体进行混合,得到混合物A;
步骤二、将引发剂质量的70%-85%用去离子水溶解,配置质量浓度为20%的水溶液;
步骤三、将剩余的去离子水、生物基乳化剂、天然油脂磺化油加入反应釜中,搅拌均匀,开始升温至40-45,℃加入剩余的引发剂和混合物A质量的1/20-1/15,然后升温至75-82℃,稳定20-30min;
步骤四、将步骤一中得到的混合物A的剩余部分和步骤二中的引发剂水溶液分别同时滴加到步骤二所述的反应釜中;
步骤五、降温至60-65℃,将松香基氨基酸表面活性剂、木质素-糠醛生物基树脂加入反应釜中,混合均匀;
步骤六、降温至45℃以下在反应釜中加入pH调节剂和消泡剂,搅拌,过滤得到生物基无氟防水剂。
所述的步骤一中,搅拌速度为800-1500rpm,搅拌时间为45-60min;
单体借助乳化剂的乳化作用,均匀分散在水中。分散越均匀稳定,后面的聚合反应越顺利。如果乳液有分层或沉淀现象,后面聚合反应的温度会不稳定,可能冲破反应上限,会产生很多滤渣。
所述步骤三中,搅拌转速为50-200rpm;
所述步骤四中,滴加时间为120-180min,78-82℃保温时间150-200min;
聚合反应的滴加速度不能太快,太快聚合反应温度可能会瞬间升高突破上限,之后温度回落,温度的起伏会产生滤渣。
所述步骤五中,混合时进行搅拌,搅拌时间15-30min;
所述步骤六中,混合时进行搅拌,搅拌转速为20-50rpm,搅拌时间为10-30min,过滤得到生物基无氟防水剂。
优选地,生物基单体为生物基甲基丙烯酸十八烷基酯、生物基丙烯酸十八烷基酯中的至少一种;
生物基单体选择15%-25%,当单体低于15%时,无氟防水剂成膜过软,不符合使用要求;当软单体大于25%时,无氟防水剂成膜脆性过大,易结皮成渣。
生物基甲基丙烯酸十八烷基酯、生物基丙烯酸十八烷基酯,是由生物基丙烯酸或者生物基甲基丙烯酸和生物基十八醇化学反应酯化得到的,生物基十八醇是在铬酸铜催化下由生物基硬脂酸加氢而制得的。因此生物基甲基丙烯酸十八烷基酯、生物基丙烯酸十八烷基酯的原料来源于生物基原料。
优选地,所述的功能性单体为甲基丙烯酰胺、甲基丙烯酸羟乙酯、甲基丙烯酰吗啉、丙烯酸羟乙酯中的至少一种或任意组合;
甲基丙烯酰胺交联性能优异,生产的无氟防水剂防水性能好,产品渗透性差,亲水性能一般;甲基丙烯酸羟乙酯交联性能一般,但是亲水性能好,防水性能一般;两者搭配使用,产品可以得到合适的亲水性能和防水效果。
优选地,所述的引发剂为偶氮二异丁脒盐酸盐、过硫酸铵、过硫酸钾中的至少一种,优选偶氮二异丁脒盐酸盐;
所述的引发剂偶氮二异丁脒盐酸盐,为低温引发剂,可以在45℃左右分解反应产生自由基,促发聚合反应。用量为0.01%-0.4%,当催化剂低于0.01%时,反应速度缓慢,升温保温时间加长;当催化剂大于0.4%时,反应速度太快,不好控制,反应时容易产生爆聚。
优选地,所述的生物基乳化剂为腰果酚聚氧乙烯醚NSS1305、NSS1305A、NSS1308、十八烷基三甲基溴化铵中的至少一种;
腰果酚聚氧乙烯醚是良好生物基非离子乳化剂,十八烷基三甲基溴化铵是生物基阴离子乳化剂,阴非离子乳化剂的共同作用,有利于单体乳液的稳定性能;
优选地,所述的天然油脂磺化油为天然磺化菜籽油、天然磺化蓖麻油、硫酸化天然牛蹄油中的至少一种,优选天然磺化菜籽油;
此为阴离子表面活性剂,与上述生物基乳化剂非离子表面活性剂腰果酚聚氧乙烯醚协同作用,使单体均匀稳定的分散在乳液中,天然磺化菜籽油与NSS 1305的质量比为1:(1.1-1.3)。
优选地,所述pH调节剂为氨水、液碱、碳酸钠中至少一种,优选液碱;
无氟防水剂高温定型时不会产生氨水气味,污染工作环境,液碱中NaOH的质量百分比为32.5%。
优选地,所述的消泡剂为聚氧丙基聚氧乙基甘油醚、聚醚改性聚硅氧烷类中的至少一种,优选聚醚改性聚硅氧烷CD-1116M。
所述CD-1116M能够在高温起泡体系中快速的渗透到泡沫内部,破坏泡沫的稳定性,从而达到消泡的效果。
一种生物基无氟防水剂的应用,将生物基无氟防水剂应用到织物的后整理中,包括如下步骤:
S1,将生物基无氟防水剂与水进行混合,得到工作液,工作液的浓度为50-100g/L;
S2,将织物在步骤S1得到的工作液中进行浸轧处理,带液率为60-80%,然后进行烘干和定型。
优选地,所述S2中,浸轧处理为一浸一轧,轧辊压力为0.15-0.25Mpa,烘干定型温度为150-180℃,烘干时间为60-120s;
优选地,所述织物为全棉织物、棉及聚酰胺纤维的混织物、棉及聚酯纤维的混织物、天丝中的至少一种,优选全棉梭织布。
一种生物基无氟防水剂,采用本发明所述的原料和制备方法制备而成。
一种生物基无氟防水剂的应用,其中,将本发明所述的生物基无氟防水剂或者本发明任意方法制备得到的生物基无氟防水剂用于纺织物的后整理。
有益效果
(1)本发明加入生物基单体,代替传统的化石碳基丙烯酸化合物。生物基单体使用植物碳生产,从而提高了可再生碳含量,产品具有超低气味、低VOC、环保安全等优异性能。
(2)本发明引入了松香基氨基酸表面活性剂,这是一种生物基的两性表面活性剂。松香是一种丰富存在于自然界中的再生性资源,其主要成分是树脂酸,其分子结构中庞大的非极性三环结构具有良好的疏水性,而极性的羧基部分又具有亲水性,通过化学法、酶法、化学酶法等方法嵌入天然谷氨酸、肌氨酸以及多肽合成一系列松香酸-N-酰基氨基酸类表面活性剂,具有污性好、耐硬水、对酸碱稳定,并具有杀菌、防腐、抗静电等性能。
(3)本发明加入了天然油脂磺化油,这是一种以天然油脂为主要原料,采用三氧化硫气体磺化工艺进行改性,再与其他必要组分复配而成的阴离子型磺化油加脂剂,是一种优良的阴离子表面活性剂,渗透性能优异,提高亲水性能和抗静电性能;可减少织物间,纤维与纤维间的摩擦作用,同时可以改善布面手感。
(4)本发明加入了木质素-糠醛生物基树脂,这是一种糠醛类的生物基树脂。糠醛是一种可由生物质转化制备的重要化工原料。木质素是一种从农业或林业残留物或造纸制浆废水中获得的生物聚合物,是唯一的芳香族天然生物聚合物。通过酶解木质素反应,木质素中的甲氧基去甲基化转化为酚羟基产物,得到高反应活性纳米木质素。用糠醛完全替代甲醛,与高反应活性纳米木质素反应合成木质素-糠醛生物基树脂。这种树脂树脂可在纤维表面交联网状成膜的功能,使纤维表面包裹一层耐磨的树脂膜,减弱纤维间的滑移,绑纱效果好;同时,树脂均匀地交联凝聚在纱线的表层,使纤维端粘附于纱线上,摩擦时不易起球。帮助丙烯酸树脂在织物表面成膜,提高织物抗皱、防静电和提高防水等性能。
(5)本发明中采用的生物基单体、生物基乳化剂、天然油脂磺化油、松香基氨基酸表面活性剂和木质素-糠醛生物基树脂均是来源于天然,无毒无害,生物降解迅速彻底的产品,对环境无污染;同时,产品作用温和,纺织品经处理后损伤小。实现产业的绿色可持续发展。
(6)本发明属于纺织工业印染生产中纺织品印染技术领域,尤其是涉及一种生物基无氟防水剂及其制备方法和应用。在本发明中,首先,在反应中加入了生物基单体,代替传统的化石碳基丙烯酸单体;其次,引入了松香基氨基酸表面活性剂,这是一种生物基的两性表面活性剂,具有污性好、耐硬水、对酸碱稳定,并具有杀菌、防腐、抗静电等性能;最后,在反应后加入了木质素-糠醛生物基树脂,这是一种新型糠醛类的生物基树脂,树脂会均匀地交联在纱线表层,使纤维末梢粘附于纱线上,而且树脂较强的粘合力可以对纤维进行粘结,以限制其移动,提高织物抗皱、防静电和防水等性能。防水处理后的织物黄变小,抗静电性能、抗起毛球性能和防水性能好,手感柔软不粗糙。本发明制成的无氟防水剂原料来源于生物基产品,在自然环境中可以完全生物降解,环保安全,提升了产品的可再生及环境友好价值,具有显著的社会效益和广阔的市场前景。
具体实施方式
为使本发明的目的、技术方案及优点更加清楚、明确,以下列举实施例对本发明进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。
下面通过具体实施例对本发明进行详细说明。
实施例1
(1)将114g水、21g NSS1305、6g十八烷基三甲基溴化铵、18g天然磺化菜籽油、120g生物基甲基丙烯酸十八烷基酯、120g生物基丙烯酸十八烷基酯、20g甲基丙烯酸丁酯、30g烷基烯酮二聚体、10g甲基丙烯酰胺、10g甲基丙烯酸羟乙酯依次投入高位混合罐1中,高速搅拌为不透明稳定乳液混合物A;
(2)称取1.6g偶氮二异丁脒盐酸盐,用6.4g水充分溶解,配置成质量浓度为20%的引发剂水溶液B;
(3)反应釜1中加入345.6g水、14g NSS1305、4g十八烷基三甲基溴化铵、12g天然磺化菜籽油,搅拌升温至40,℃加入0.4g偶氮二异丁脒盐酸盐和25g混合物A,迅速升温至75-82℃,持温反应一段时间20-30min;
(4)待反应釜1中溶液变蓝澄清,聚合反应引发后开始滴加剩余混合物A和引发剂水溶液B,120min滴加完毕后在80℃下保温150min;
(5)降温冷却至60,℃将40g松香基氨基酸表面活性剂、100g木质素-糠醛生物基树脂加入反应釜1中,搅拌时间为30min,降温至40;℃
(6)将5g液碱、2g CD-1116M加入反应釜1中,搅拌时间为15min,过滤得到无氟防水剂1。
实施例2
(1)将114g水、21g NSS1305、6g十八烷基三甲基溴化铵、18g天然磺化菜籽油、150g生物基甲基丙烯酸十八烷基酯、100g生物基丙烯酸十八烷基酯、20g甲基丙烯酸丁酯、30g甲基丙烯酸甲酯、10g甲基丙烯酰胺、10g甲基丙烯酸羟乙酯依次投入高位混合罐1中,高速搅拌为不透明稳定乳液混合物A;
(2)称取1.6g偶氮二异丁脒盐酸盐,用6.4g水充分溶解,配置成质量浓度为20%的引发剂水溶液B;
(3)反应釜1中加入335.6g水、14g NSS1305、4g十八烷基三甲基溴化铵、12g天然磺化菜籽油,搅拌升温至40,℃加入0.4g偶氮二异丁脒盐酸盐和25g混合物A,迅速升温至75-82℃,持温反应一段时间20-30min;
(4)待反应釜1中溶液变蓝澄清,聚合反应引发后开始滴加剩余混合物A和引发剂水溶液B,120min滴加完毕后在80℃下保温150min;
(5)降温冷却至60,℃将40g松香基氨基酸表面活性剂、100g木质素-糠醛生物基树脂加入反应釜1中,搅拌时间为30min,降温至40;℃
(6)将5g液碱、2g CD-1116M加入反应釜1中,搅拌时间为15min,过滤得到无氟防水剂2。
实施例3
(1)将114g水、21g NSS1305、6g十八烷基三甲基溴化铵、18g天然磺化菜籽油、100g生物基甲基丙烯酸十八烷基酯、150g生物基丙烯酸十八烷基酯、20g甲基丙烯酸甲酯、30g烷基烯酮二聚体、10g甲基丙烯酰胺、10g甲基丙烯酸羟乙酯依次投入高位混合罐1中,高速搅拌为不透明稳定乳液混合物A;
(2)称取1.6g偶氮二异丁脒盐酸盐,用6.4g水充分溶解,配置成质量浓度为20%的引发剂水溶液B;
(3)反应釜1中加入335.6g水、14g NSS1305、4g十八烷基三甲基溴化铵、12g天然磺化菜籽油,搅拌升温至40,℃加入0.4g偶氮二异丁脒盐酸盐和25g混合物A,迅速升温至75-82℃,持温反应一段时间20-30min;
(4)待反应釜1中溶液变蓝澄清,聚合反应引发后开始滴加剩余混合物A和引发剂水溶液B,120min滴加完毕后在80℃下保温150min;
(5)降温冷却至60,℃将40g松香基氨基酸表面活性剂、100g木质素-糠醛生物基树脂加入反应釜1中,搅拌时间为30min,降温至40;℃
(6)将5g液碱、2g CD-1116M加入反应釜1中,搅拌时间为15min,过滤得到无氟防水剂3。
无氟防水剂的优劣评价最主要的就是织物的防水性能,及耐洗牢度,还需要产品稳定、对织物色光影响和抗黄变性能等做综合评价。
下面结合对比例对本发明做进一步说明,所述实施例和对比例仅为帮助理解本发明,不应视为对本发明的具体限制。
对比例1
市售3号防水剂,此为市面常用防水剂。
一、物理特性测试
对通过本发明实施例1-3制得的生物基无氟防水剂进行物理特性测试,结果如表1所示:
表1
由表1可知,通过本发明制备出来的生物基无氟防水剂产品稳定,含量高,安全性好,是一种可用于纺织品加工的整理剂,安全性高,具有良好的应用前景。
二、无氟防水剂应用性能测试
将上述实施例1-3所制得的生物基无氟防水剂和市面常用的防水剂对比例1进行对比测试。
2.1整理剂应用工艺:
织物:100%全棉梭织布
工艺:浸轧焙烘
生物基无氟防水剂实施例1-3的应用,浸轧焙烘工艺:
S1将上述实施例1-3所制得的生物基无氟防水剂和市面常用的防水剂与水进行混合,得到工作液,工作液的浓度为80g/L;
S2.将织物在步骤S1得到的工作液中进行一浸一轧处理,带液率为60-80%,然后进行160℃烘干定型,烘干时间为90s;
S3.回潮评价防水性能。
2.2将实施例和对比例分别对其黄变、防水性能进行测试:
(1)柔软性能评价方法
手感评价:对两种布样进行手触摸法进行评价,将原布手感评定为1级,手感评定最好的定位为5级。数值越大,表示手感越好,测试结果见表2。
(2)白度、色光评价方法
用Datacolor测色仪进行测试。与未处理布样进行白度对比,白度变化越大,即黄变越大,测试结果见表2;
(3)防水测试
用圆形铁环把布绷紧,与出水口成45°夹角,出水口距离布面中心15cm,100ml水垂直均速洒下,水洒完后,磕去布面的浮水,观察被测布面的水痕斑点个数和大小,进行评分。100分为无水痕无斑点,分数越低说明防水效果越差。
表2
整理剂 | 手感等级 | 白度 | 防水评分 |
原布 | 1 | 77.02 | 0 |
实施例1 | 4 | 76.18 | 95 |
实施例2 | 4 | 75.37 | 100 |
实施例3 | 4 | 74.85 | 100 |
对比例1 | 3-4 | 65.21 | 95 |
由表2可以看出,本实施例1、2、3产品优于或接近市场上常规产品,不易色变,具有良好的抗黄变效果。同时,处理后的织物还具有极佳的手感和防水性能。
综上所述,本发明提供一种生物基无氟防水剂及其制备方法,首先,在反应中加入了生物基单体,代替传统的化石碳基丙烯酸化合物;其次,引入了松香基氨基酸表面活性剂,这是一种生物基的两性表面活性剂,具有污性好、耐硬水、对酸碱稳定,并具有杀菌、防腐、抗静电等性能;最后,在反应后加入了木质素-糠醛生物基树脂,这是一种新型糠醛类的生物基树脂,树脂会均匀地交联在纱线表层,使纤维末梢粘附于纱线上,而且树脂较强的粘合力可以对纤维进行粘结,以限制其移动,水洗后织物不掉纱不断纱。防水剂整理后的织物黄变小,防水性能好,手感柔软不粗糙。本发明制成的无氟防水剂原料来源于生物基产品,在自然环境中可以完全生物降解,环保安全,提升了产品的可再生及环境友好价值,
申请人声明,本发明通过上述实施例来说明本发明的生物基无氟防水剂及制备方法和应用,但本发明并不局限于上述详细方法,即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (8)
1.一种生物基无氟防水剂,其特征在于:
该无氟防水剂的原料包括生物基单体、基体单体、功能性单体、引发剂、生物基乳化剂、天然油脂磺化油、松香基氨基酸表面活性剂、木质素-糠醛生物基树脂、pH调节剂、消泡剂和去离子水;
以该无氟防水剂的原料的总质量为100%计算,各组份的质量百分含量为:
生物基单体 15%-25%
基体单体 2%-5%
功能性单体 1%-3%
引发剂 0.01%-0.4%
生物基乳化剂 1%-5%
天然油脂磺化油 1%-5%
松香基氨基酸表面活性剂 1%-5%
木质素-糠醛生物基树脂 5%-15%
pH调节剂 0.01%-1%
消泡剂 0.01%-0.5%
余量为去离子水。
2.根据权利要求1所述的一种生物基无氟防水剂,其特征在于:
所述的生物基单体为生物基甲基丙烯酸十八烷基酯、生物基丙烯酸十八烷基酯中的至少一种;
所述的基体单体为甲基丙烯酸丁酯、甲基丙烯酸甲酯、烷基烯酮二聚体、丙烯酸十二烷基酯中的至少一种;
所述的功能性单体为甲基丙烯酰胺、甲基丙烯酸羟乙酯、甲基丙烯酰吗啉、丙烯酸羟乙酯中的至少一种;
所述的引发剂为偶氮二异丁脒盐酸盐、过硫酸铵、过硫酸钾中的至少一种;
所述的生物基乳化剂为腰果酚聚氧乙烯醚NSS1305、NSS1305A、NSS1308、十八烷基三甲基溴化铵中的至少一种;
所述的天然油脂磺化油为天然磺化菜籽油、天然磺化蓖麻油、硫酸化天然牛蹄油中的至少一种;
所述pH调节剂为氨水、液碱、碳酸钠中至少一种;
所述的消泡剂为聚氧丙基聚氧乙基甘油醚、聚醚改性聚硅氧烷类中的至少一种。
3.一种生物基无氟防水剂的制备方法,其特征在于步骤包括:
步骤一、将去离子水质量的20%-30%、生物基乳化剂质量的55%-70%、天然油脂磺化油质量的55%-65%、生物基单体、基体单体、功能性单体进行混合,得到混合物A;
步骤二、将引发剂质量的70%-85%用去离子水溶解,配置质量浓度为20%的水溶液;
步骤三、将剩余的去离子水、生物基乳化剂、天然油脂磺化油加入反应釜中,搅拌均匀,开始升温至40-45,℃加入剩余的引发剂和混合物A质量的1/20-1/15,然后升温至75-82℃,稳定20-30min;
步骤四、将步骤一中得到的混合物A的剩余部分和步骤二中的引发剂水溶液分别同时滴加到步骤二所述的反应釜中;
步骤五、降温至60-65℃,将松香基氨基酸表面活性剂、木质素-糠醛生物基树脂加入反应釜中,混合均匀;
步骤六、降温至45℃以下在反应釜中加入pH调节剂和消泡剂,搅拌,过滤得到生物基无氟防水剂。
4.根据权利要求3所述的一种生物基无氟防水剂的制备方法,其特征在于:
所述步骤一中,搅拌速度为800-1500rpm,搅拌时间为45-60min。
5.根据权利要求4所述的一种生物基无氟防水剂的制备方法,其特征在于:
所述步骤三中,搅拌转速为50-200rpm;
所述步骤四中,滴加时间为120-180min,78-82℃保温时间150-200min;
所述步骤五中,搅拌时间15-30min;
所述步骤六中,搅拌转速为20-50rpm,搅拌时间10-30min。
6.一种生物基无氟防水剂的应用,其特征在于:将生物基无氟防水剂应用到织物的后整理中,包括如下步骤:
S1,将权利要求1-2任一所述的生物基无氟防水剂或者是权利要求3-5任一方法制备得到的生物基无氟防水剂与水进行混合,得到工作液,工作液的浓度为50-100g/L;
S2,将织物在步骤S1得到的工作液中进行浸轧处理,带液率为60%-80%,然后进行烘干和定型。
7.根据权利要求6所述的生物基无氟防水剂的应用,其特征在于:
所述的步骤S2中,浸轧处理为一浸一轧,轧辊压力为0.15-0.25Mpa,烘干定型温度为150-180℃,烘干时间为60-120s。
8.根据权利要求6所述的生物基无氟防水剂的应用,其特征在于:
所述的步骤S2中,所述织物为全棉织物、棉及聚酰胺纤维的混织物、棉及聚酯纤维的混织物、天丝中的至少一种。
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