CN110218440B - 一种可紫外固化的蓖麻油基抗菌水性聚氨酯乳液的制备方法 - Google Patents
一种可紫外固化的蓖麻油基抗菌水性聚氨酯乳液的制备方法 Download PDFInfo
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Abstract
本发明公开了一种可紫外固化的蓖麻油基抗菌水性聚氨酯乳液的制备方法,首先通过甲基丙烯酸缩水甘油醚(GMA)对生物相容性良好的ε‑聚赖氨酸(ε‑PL)进行改性,得到含有活泼双键且具有抗菌性能的材料ε‑PL‑GMA;然后用蓖麻油代替传统合成水性聚氨酯的多元醇或聚醚类,同时加入甲基丙烯酸羟乙酯(HEMA)进行反应,得到可紫外固化的蓖麻油基水性聚氨酯乳液;随后加入ε‑PL‑GMA的水溶液,以及光引发剂,紫外固化后即可得到蓖麻油基抗菌型水性聚氨酯膜。本发明采用天然材料蓖麻油合成抗菌型水性聚氨酯乳液,具有抗菌性能的同时具有可紫外固化功能,抗菌成分安全性高,且紫外固化能减少固化时间和挥发性有机化合物(VOCS)的排放。
Description
技术领域
本发明属于聚氨酯技术领域,具体涉及一种可紫外固化的蓖麻油基抗菌水性聚氨酯乳液的制备方法。
背景知识
水性聚聚氨酯(WPU)具有优异的耐化学性、可调的热机械性能和良好的加工性能,是用途最广泛的高分子材料之一,在涂料、粘合剂、服装、涂料和泡沫塑料等领域有着广泛的应用。传统聚氨酯产品通常含有大量挥发性有机化合物(VOCs),这些物质对生产者和使用者的健康构成很大威胁。随着越来越严格的法规的出台和消费者对降低VOCs的要求,目前环保水性聚氨酯在全球范围内兴起,旨在部分或完全取代溶剂型聚氨酯。
目前,合成水性聚氨酯的原料(多元醇、异氰酸酯、扩链剂)大多来源于石化原料,这些原料被广泛认为是不可再生的,随着世界原油储量的枯竭和环境问题的日益严重,全球范围内致力于寻找一种可再生资源(如纤维素、天然油脂、木质素等),用生物基聚氨酯取代石油基聚氨酯,蓖麻油作为一种典型的可再生生物质能资源,因其成本低、易得性好,在水性聚氨酯合成中具有广阔的应用前景。
水性聚氨酯应用范围很广,但其在实际使用过程中经常受到细菌等微生物的干扰,这限制了水性聚氨酯材料的进一步推广,因此很有必要研发具有抗菌性能的水性聚氨酯材料。ε-聚赖氨酸是由微生物大量生产的氨基酸同型聚合物,其具有光谱的杀菌性,水容性,生物相容性,安全性等优点,是一种理想的抗菌材料。
紫外固化技术,具有固化速率快、效率高、施工周期短、成本低和VOCs排放低等优点,一直是环保化学发展方向之一。
发明内容
本发明的目的是提供一种可紫外固化的蓖麻油基抗菌水性聚氨酯乳液的制备方法。本发明通过紫外固化技术,用甲基丙烯酸缩水甘油醚改性的ε-聚赖氨酸与蓖麻油基水性聚氨酯结合,能提高蓖麻油基水性聚氨酯的抗菌性能,使水性聚氨酯更好地用于抗菌领域。
本发明可紫外固化的蓖麻油基抗菌水性聚氨酯乳液的制备方法,首先通过甲基丙烯酸缩水甘油醚(GMA)对生物相容性良好的ε-聚赖氨酸(ε-PL)进行改性,得到含有活泼双键且具有抗菌性能的材料ε-PL-GMA;然后用天然可再生材料蓖麻油(CO)代替传统合成水性聚氨酯的多元醇或聚醚类,同时加入甲基丙烯酸羟乙酯(HEMA)进行反应,得到可紫外固化的蓖麻油基水性聚氨酯乳液;随后向上述可紫外固化的蓖麻油基水性聚氨酯乳液中加入ε-PL-GMA的水溶液,超声分散,得到可紫外固化的蓖麻油基抗菌型水性聚氨酯乳液;最后向上述聚氨酯乳液中加入光引发剂,干燥去除水分,紫外固化后即可得到蓖麻油基抗菌型水性聚氨酯膜。
具体包括如下步骤:
步骤1:将甲基丙烯酸缩水甘油醚(GMA)与ε-聚赖氨酸反应获得ε-PL-GMA抗菌材料;
步骤2:将二异氰酸酯与多元醇亲水扩链剂加入到反应器中进行反应;
步骤3:向步骤2的反应体系中加入甲基丙烯酸羟乙酯(HEMA)继续反应,并用丁酮调节粘度范围在16.0mPa·s~30.0mPa·s,得到预聚物;
步骤4:向步骤3获得的预聚物中加入蓖麻油以及催化剂进行反应,反应结束后降温至40℃以下,加入成盐剂反应5min,随后加入去离子水,通过高速剪切乳化,再减压蒸馏去除丁酮,得到固含量30wt%的可紫外固化的蓖麻油基水性聚氨酯乳液;
步骤5:向步骤4获得的可紫外固化的蓖麻油基水性聚氨酯乳液中加入步骤1获得的抗菌材料水溶液,超声分散(5-10min),得到可紫外固化的蓖麻油基抗菌型水性聚氨酯乳液;
步骤6:向步骤5获得的聚氨酯乳液中加入聚氨酯乳液固含量3%的光引发剂,干燥去除水分,在紫外固化箱中照射60s,即可得到蓖麻油基抗菌型水性聚氨酯膜。
进一步地,步骤1中,首先将ε-聚赖氨酸溶于甲醇中,然后加入GMA,反应摩尔比为1:3,反应温度为40℃,反应时间72h,反应产物需减压蒸馏干燥。
步骤2中,所述二异氰酸酯为异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯中的一种或两者按摩尔比1:1混合,所述二异氰酸酯的添加质量为树脂总质量的35%-40%;所述多元醇亲水扩链剂为二羟甲基丙酸、1,4-丁二醇中的一种或两者按摩尔比1:1-3混合,所述多元醇亲水扩链剂的添加质量为树脂总质量的9-12%。所述树脂总质量为二异氰酸酯、多元醇亲水扩链剂、甲基丙烯酸羟乙酯、蓖麻油、催化剂以及成盐剂的质量总和。
步骤2中,反应温度为60℃,反应时间为2h,反应需在氮气氛围中进行。
步骤3中,步骤2的反应体系降温至35℃以下后再加入HEMA(总树酯的11%~15%),反应温度50℃,反应时间2h。
步骤4中,所述蓖麻油在添加前需提前进行除水处理,在120℃下减压真空除水2h;所述蓖麻油的添加质量为树脂总质量的28%-32%。
步骤4中,反应温度为65℃,反应时间为3h,反应需在氮气氛围中进行。
步骤4中,所述催化剂为辛酸亚锡,加入量总树脂质量的0.025%~0.075%。
步骤4中,所述成盐剂为三乙胺,其添加量和DMPA物质的量相等。
步骤4中,去离子水的添加质量为树脂总质量的两倍。
步骤5中,所述抗菌材料按照1:20的质量比配制成抗菌材料水溶液后加入步骤4获得的蓖麻油基水性聚氨酯乳液中,添加质量为蓖麻油基水性聚氨酯乳液质量的1%-5%。
本发明可紫外固化的蓖麻油基抗菌水性聚氨酯乳液可应用在水性涂料和抗菌医疗设施中。
与现有技术相比,本发明的有益效果体现在:
1、用生物可再生资源蓖麻油部分代替聚醚多元醇或聚酯多元醇,符合绿色发展理念,为水性聚氨酯的发展提供新的可能。
2、用毒理性小,生物相容性好的抗菌剂改性水性聚氨酯,使其获得抗菌性能,扩大水性聚氨酯的应用范围。
3、引入活泼双键使水性聚氨酯乳液可以紫外固化,减少乳液固化时间,减少VOCS的排放。
附图说明
图1是实施例1制得的抗菌型水性聚氨酯的红外谱图。由图1可知,红外谱图主要峰为:3320cm-1,3078cm-1,2931cm-1,1630cm-1,1520cm-1,1452cm-1,1230cm-1。
图2是采用贴膜法测试未添加抗菌剂的聚氨酯乳液的抗菌性能。由图2可知,未添加抗菌剂的聚氨酯乳液不具有抗菌性能。
图3是采用贴膜法测试本发明聚氨酯材料的抗菌性能。本发明聚氨酯膜对金黄色葡萄球菌的抑菌率为90%,检测标准为(GB/T 21866-2008),说明本发明聚氨酯乳液具有优异的抗菌性能。
图4是采用贴膜法测试本发明聚氨酯材料的抗菌性能。本发明聚氨酯膜对金黄色葡萄球菌的抑菌率为95%,检测标准为(GB/T 21866-2008),说明本发明聚氨酯乳液具有优异的抗菌性能。
图5是采用贴膜法测试本发明聚氨酯材料的抗菌性能。本发明聚氨酯膜对金黄色葡萄球菌的抑菌率为95%,检测标准为(GB/T 21866-2008),说明本发明聚氨酯乳液具有优异的抗菌性能。
图6是采用贴膜法测试本发明聚氨酯材料的抗菌性能。本发明聚氨酯膜对金黄色葡萄球菌的抑菌率为99%,检测标准为(GB/T 21866-2008),说明本发明聚氨酯乳液具有优异的抗菌性能。
具体实施方式
下面结合实例对本发明进行进一步分析,但本实验实施方式不限于此。
实施例1:可紫外固化蓖麻油基抗菌水性聚氨酯乳液的制备
1、将10.74gε-聚赖氨酸加入到反应器中,加入甲醇溶液超声至完全溶解,再加入1.278g甲基苯烯酸缩水甘油醚,在40℃下反应72h,反应结束后减压蒸馏干燥得到抗菌材料,以下相同。
2、将5.04g六亚甲基二异氰酸酯、6.66g异佛尔酮二异氰酸酯和4.02g二羟甲基丙酸加入到三口烧瓶中,在氮气氛围下60℃反应2h。
3、将步骤2的反应体系降温至35℃以下,加入3.9g甲基丙烯酸羟乙酯,在50℃下反应2h;
4、将体系降温至40℃以下,加入9.3g已于120℃下,真空除水2h的蓖麻油,再加入一滴辛酸亚锡催化剂,2mL丁酮调节粘度,体系在氮气氛围下65℃反应3h;将体系降温至40℃以下,加入4.47g三乙胺,反应5min,加入67g去离子水(固含量为33wt%),高速剪切30min,减压蒸馏去除丁酮,得到可紫外固化的蓖麻油基水性聚氨酯乳液。
5、向步骤4获得的可紫外固化的蓖麻油基水性聚氨酯乳液中加入步骤1获得的抗菌材料水溶液,甲基丙烯酸羟乙酯改性的ε-聚赖氨酸抗菌剂与水质量比为1:20,以下相同;抗菌剂的用量为0.2g,抗菌剂的用量占水性聚氨酯的1%,超声分散5min,得到可紫外固化的蓖麻油基抗菌水性聚氨酯乳液,固含量33%,以下相同。
6、取上述乳液加入固含量3%的光引发剂,超声分散,铺入聚四氟乙烯板中,自然干燥去除水分,在紫外固化机下照射60s,得到紫外固化蓖麻油基抗菌水性聚氨酯膜。
对本发明实施例1制得的抗菌型水性聚氨酯进行红外检测,检测结果如图1所示,由图1可知,红外谱图主要峰为:3320cm-1,3078cm-1,2931cm-1,1630cm-1,1520cm-1,1452cm-1,1230cm-1。
采用贴膜法测试抗菌性能,如图2未添加抗菌剂聚氨酯乳液不具有抗菌性能。
实施例2:可紫外固化蓖麻油基抗菌水性聚氨酯乳液的制备
1、将3.36g六亚甲基二异氰酸酯,4.44g异佛尔酮二异氰酸酯,1.34g二羟甲基丙酸,0.9g 1,4-丁二醇,加入到三口烧瓶中,在氮气氛围下60℃反应2h。
2、将体系降温至35℃以下,加入2.6g甲基丙烯酸羟乙酯,在50℃下反应2h。
3、将体系降温至40℃以下,加入6.22g已于120℃下,真空除水2h的蓖麻油,再加入一滴辛酸亚锡催化剂,2mL丁酮调节粘度,体系在氮气氛围下65℃反应3h。
4、将体系降温至40℃以下,加入1g三乙胺,反应5min;加入40g去离子水(固含量为33wt%),高速剪切30min,减压蒸馏去除丁酮,得到可紫外固化的蓖麻油基水性聚氨酯乳液。
5、加入抗菌分散液(甲基丙烯酸羟乙酯改性的ε-聚赖氨酸抗菌剂与水质量比为1:20,以下相同),抗菌剂的用量为0.2g,抗菌剂的用量占水性聚氨酯的2%,超声分散5min。得到紫外固化蓖麻油基抗菌水性聚氨酯乳液,固含量33%,以下相同。
6、取上述乳液加入固含量3%的光引发剂,超声分散,铺入聚四氟乙烯板中,自然干燥去除水分,在紫外固化机下照射60s,得到紫外固化蓖麻油基抗菌水性聚氨酯膜。
红外谱图主要峰为:3325cm-1,3060cm-1,2930cm-1,1620cm-1,1520cm-1,1450cm-1,1230cm-1。
采用贴膜法测试抗菌性能,如图3所制聚氨酯膜对金黄色葡萄球菌的抑菌率为90%检测标准为(GB/T 21866-2008),说明发明聚氨酯乳液具有优异抗菌性能。
实施例3:可紫外固化蓖麻油基抗菌水性聚氨酯乳液的制备
1、将3.36g六亚甲基二异氰酸酯,4.44g异佛尔酮二异氰酸酯,0.67g二羟甲基丙酸,1.35g1,4-丁二醇加入到三口烧瓶中,在氮气氛围下60℃反应2h。
2、将体系降温至35℃以下,加入2.6g甲基丙烯酸羟乙酯,在50℃下反应2h.
3、将体系降温至40℃以下,加入6.22g已于120℃下,真空除水2h的蓖麻油,再加入一滴辛酸亚锡催化剂,2mL丁酮调节粘度,体系在氮气氛围下65℃反应3h。
4、将体系降温至40℃以下,加入0.5g三乙胺,反应5min;加入40g去离子水(固含量为33wt%),高速剪切30min,减压蒸馏去除丁酮,得到可紫外固化的蓖麻油基水性聚氨酯乳液。
5、随后,加入抗菌分散液(甲基丙烯酸羟乙酯改性的ε-聚赖氨酸抗菌剂与水质量比为1:20,以下相同),抗菌剂的用量为0.3g,抗菌剂的用量占水性聚氨酯的3%,超声分散5min。得到紫外固化蓖麻油基抗菌水性聚氨酯乳液。固含量33%,以下相同。
6、取上述乳液加入固含量3%的光引发剂,超声分散,铺入聚四氟乙烯板中,自然干燥去除水分,在紫外固化机下照射60s,得到紫外固化蓖麻油基抗菌水性聚氨酯膜。
红外谱图主要峰为:3320cm-1,3060cm-1,2915cm-1,1614cm-1,1525cm-1,1450cm-1,1235cm-1。
采用贴膜法测试抗菌性能,如图4所制聚氨酯膜对金黄色葡萄球菌的抑菌率为95%检测标准为(GB/T 21866-2008),说明发明聚氨酯乳液具有优异抗菌性能。
实施例4:可紫外固化蓖麻油基抗菌水性聚氨酯乳液的制备
1、将6.72g六亚甲基二异氰酸酯,4.44g异佛尔酮二异氰酸酯,2.01g二羟甲基丙酸,1.35g1,4-丁二醇加入到三口烧瓶中,在氮气氛围下60℃反应2h。
2、将体系降温至35℃以下,加入3.9g甲基丙烯酸羟乙酯,在50℃下反应2h.
3、将体系降温至40℃以下,加入9.3g已于120℃下,真空除水2h的蓖麻油,再加入一滴辛酸亚锡催化剂,2mL丁酮调节粘度,体系在氮气氛围下65℃反应3h。
4、将体系降温至40℃以下,加入2.235g三乙胺,反应5min;加入60g去离子水(固含量为33wt%),高速剪切30min,减压蒸馏去除丁酮,得到可紫外固化的蓖麻油基水性聚氨酯乳液。
5、随后,加入抗菌分散液(甲基丙烯酸羟乙酯改性的ε-聚赖氨酸抗菌剂与水质量比为1:20,以下相同),抗菌剂的用量为0.3g,抗菌剂的用量占水性聚氨酯的3%,超声分散5min。得到紫外固化蓖麻油基抗菌水性聚氨酯乳液。固含量33%,以下相同。
6、取上述乳液加入固含量3%的光引发剂,超声分散,铺入聚四氟乙烯板中,自然干燥去除水分,在紫外固化机下照射60s,得到紫外固化蓖麻油基抗菌水性聚氨酯膜。
红外谱图主要峰为:3315cm-1,3065cm-1,2925cm-1,1610cm-1,1522cm-1,1460cm-1,1240cm-1。
采用贴膜法测试抗菌性能,如图5所制聚氨酯膜对金黄色葡萄球菌的抑菌率为95%检测标准为(GB/T 21866-2008),说明发明聚氨酯乳液具有优异抗菌性能。
实施例5:可紫外固化蓖麻油基抗菌水性聚氨酯乳液的制备
1、将3.36g六亚甲基二异氰酸酯,8.88异佛尔酮二异氰酸酯,2.68g二羟甲基丙,0.9g 1,4-丁二醇加入到三口烧瓶中,在氮气氛围下60℃反应2h。
2、将体系降温至35℃以下,加入2.6g甲基丙烯酸羟乙酯,在50℃下反应2h.
3、将体系降温至40℃以下,加入12.44g已于120℃下,真空除水2h的蓖麻油,再加入一滴辛酸亚锡催化剂,2mL丁酮调节粘度,体系在氮气氛围下65℃反应3h。
4、将体系降温至40℃以下,加入2.98g三乙胺,反应5min;加入67g去离子水(固含量为33wt%),高速剪切30min,减压蒸馏去除丁酮,得到可紫外固化的蓖麻油基水性聚氨酯乳液。
5、随后,加入抗菌分散液(甲基丙烯酸羟乙酯改性的ε-聚赖氨酸抗菌剂与水质量比为1:20,以下相同),抗菌剂的用量为0.5g,抗菌剂的用量占水性聚氨酯的5%,超声分散5min。得到紫外固化蓖麻油基抗菌水性聚氨酯乳液。固含量33%,以下相同。
6、取上述乳液加入固含量3%的光引发剂,超声分散,铺入聚四氟乙烯板中,自然干燥去除水分,在紫外固化机下照射60s,得到紫外固化蓖麻油基抗菌水性聚氨酯膜。
红外谱图主要峰为:3321cm-1,3060cm-1,2925cm-1,1615cm-1,1522cm-1,1460cm-1,1242cm-1。
采用贴膜法测试抗菌性能,如图6所制聚氨酯膜对金黄色葡萄球菌的抑菌率为99%检测标准为(GB/T 21866-2008),说明发明聚氨酯乳液具有优异抗菌性能。
Claims (8)
1.一种可紫外固化的蓖麻油基抗菌型水性聚氨酯膜的制备方法,其特征在于:
首先通过甲基丙烯酸缩水甘油醚对生物相容性良好的ε-聚赖氨酸进行改性,得到含有活泼双键且具有抗菌性能的材料ε-PL-GMA;然后用天然可再生材料蓖麻油代替传统合成水性聚氨酯的多元醇或聚醚类,同时加入甲基丙烯酸羟乙酯进行反应,得到可紫外固化的蓖麻油基水性聚氨酯乳液;随后向可紫外固化的蓖麻油基水性聚氨酯乳液中加入ε-PL-GMA的水溶液,超声分散,得到可紫外固化的蓖麻油基抗菌型水性聚氨酯乳液;最后向聚氨酯乳液中加入光引发剂,干燥去除水分,紫外固化后即可得到蓖麻油基抗菌型水性聚氨酯膜;包括如下步骤:
步骤1:将甲基丙烯酸缩水甘油醚与ε-聚赖氨酸反应获得ε-PL-GMA抗菌材料;
步骤2:将二异氰酸酯与多元醇扩链剂加入到反应器中进行反应;所述多元醇扩链剂为二羟甲基丙酸或者为二羟甲基丙酸和1,4-丁二醇按摩尔比1:1-3混合;
步骤3:向步骤2的反应体系中加入甲基丙烯酸羟乙酯继续反应,并用丁酮调节粘度范围在16.0mPa·s~30.0mPa·s,得到预聚物;
步骤4:向步骤3获得的预聚物中加入蓖麻油以及催化剂进行反应,反应结束后降温至40℃以下,加入成盐剂反应5min,随后加入去离子水,通过高速剪切乳化,再减压蒸馏去除丁酮,得到可紫外固化的蓖麻油基水性聚氨酯乳液;
步骤5:向步骤4获得的可紫外固化的蓖麻油基水性聚氨酯乳液中加入步骤1获得的抗菌材料水溶液,超声分散,得到可紫外固化的蓖麻油基抗菌型水性聚氨酯乳液;
步骤6:向步骤5获得的聚氨酯乳液中加入聚氨酯乳液固含量3%的光引发剂,干燥去除水分,在紫外固化箱中照射60s,即可得到蓖麻油基抗菌型水性聚氨酯膜。
2.根据权利要求1所述的制备方法,其特征在于:
步骤1中,首先将ε-聚赖氨酸溶于甲醇中,然后加入GMA,反应摩尔比为1:3,反应温度为40℃,反应时间72h,反应产物减压蒸馏干燥。
3.根据权利要求1所述的制备方法,其特征在于:
步骤2中,所述二异氰酸酯为异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯中的一种或两者按摩尔比1:1混合,所述二异氰酸酯的添加质量为树脂总质量的35%-40%;所述多元醇扩链剂的添加质量为树脂总质量的9-12%。
4.根据权利要求1或3所述的制备方法,其特征在于:
步骤2中,反应温度为60℃,反应时间为2h,反应在氮气氛围中进行。
5.根据权利要求1所述的制备方法,其特征在于:
步骤3中,步骤2的反应体系降温至35℃以下后再加入树脂总质量11%~15%的HEMA,反应温度50℃,反应时间2h。
6.根据权利要求1所述的制备方法,其特征在于:
步骤4中,所述蓖麻油的添加质量为树脂总质量的28%-32%;所述催化剂为辛酸亚锡,加入量为总树脂质量的0.025%~0.075%;所述成盐剂为三乙胺,其添加的物质的量和DMPA物质的量相等。
7.根据权利要求1或6所述的制备方法,其特征在于:
步骤4中,反应温度为65℃,反应时间为3h,反应在氮气氛围中进行。
8.根据权利要求1所述的制备方法,其特征在于:
步骤5中,所述抗菌材料按照1:20的质量比配制成抗菌材料水溶液后加入步骤4获得的蓖麻油基水性聚氨酯乳液中,添加质量为蓖麻油基水性聚氨酯乳液质量的1%-5%。
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