CN114853971A - 一种可降解水性聚氨酯及其制备方法 - Google Patents
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Abstract
本发明公开了一种可降解水性聚氨酯及其制备方法,所述可降解水性聚氨酯包括如下组分:二异氰酸酯、多元醇、内交联剂、小分子扩链剂、催化剂、亲水扩链剂、中和剂和后扩链剂。本发明通过聚己内脂二醇与聚乳酸二醇复合使用提高了单纯使用聚乳酸聚氨酯材料难于成膜,拉伸强度较低的缺点;同时采用葡萄糖作为交联剂,葡萄糖含有五个活性羟基,可提高水性聚氨酯的交联度,从而改善胶膜的耐水性和耐溶剂性;本发明的可降解水性聚氨酯工艺简单,且仅适用少量低沸点的丙酮做溶剂,易于脱除,不造成有机溶剂污染。
Description
技术领域
本发明涉及精细高分子材料技术领域,具体为一种可降解水性聚氨酯及其制备方法。
背景技术
水性聚氨酯相比于油性产品没有溶剂使用和产生,部分解决了环境污染的问题,并且改善了相关行业中工人的工作环境,但是仍存在难降解的难题,在这样的情况下,迫切要求开发快速高效可降解的材料来解决这一问题。聚乳酸(PLA)是最具代表性的生物降解材料之一。它使用可再生的植物资源(如玉米等)所提出的淀粉原料制成。淀粉原料经由发酵过程制成乳酸,再通过化学合成转换成聚乳酸。其来源广泛且价格低廉,最终又会被微生物完全降解,对环境无负担。然而,聚乳酸的来源及合成工艺决定了其相对分子质量分布较宽的特点,且聚乳酸为线性聚合物,这使得以聚乳酸为多元醇合成的树脂强度较低,在实际应用过程中有一定的局限性。
本发明的可降解水性聚氨酯在应用聚乳酸做多元醇的同时,加入聚己内酯二醇,同时用葡萄糖做交联剂合成了高强度的可降解水性聚氨酯,拓宽了聚乳酸合成水性聚氨酯的应用范围。
发明内容
针对相关技术中的问题,本发明提出的一种可降解水性聚氨酯及其制备方法,以克服现有相关技术所存在的上述技术问题,本发明的目的是通过聚己内脂二醇与聚乳酸二醇复合使用提高了单纯使用聚乳酸聚氨酯材料难于成膜,拉伸强度较低的缺点;同时采用葡萄糖作为交联剂,葡萄糖含有五个活性羟基,可提高水性聚氨酯的交联度,从而改善胶膜的耐水性和耐溶剂性;本发明的可降解水性聚氨酯工艺简单,且仅适用少量低沸点的丙酮做溶剂,易于脱除,不造成有机溶剂污染。
为实现上述目的,本发明提供如下技术方案:
一种可降解水性聚氨酯,包括按重量份数计的如下组分:二异氰酸酯80-120份、多元醇240-480份、内交联剂0.1-0.8份、小分子扩链剂1-3份、催化剂0.01-0.1份、亲水扩链剂12-24份、中和剂11-16份和后扩链剂12-24份。
优选的,所述二异氰酸酯为异佛二酮二异氰酸酯、二环己基甲烷二异氰酸酯中的一种或多种。
采用本技术方案,二异氰酸酯在合成预聚体中占15%-25%。
优选的,所述多元醇为聚己内酯二醇和聚乳酸二醇的混合物。
采用本技术方案,多元醇在合成预聚体中占65%-75%,其中聚乳酸在多元醇中的比例不低于70%。
优选的,所述内交联剂为葡萄糖。
采用本技术方案,内交联剂在合成预聚体中占0-2.5%。
优选的,所述小分子扩链剂为1,4-丁二醇、1,6-己二醇中的一种或多种。
采用本技术方案,小分子扩链剂在合成预聚体中占0.5-3%。
优选的,所述催化剂为二丁基二月硅酸锡、辛酸亚锡中的一种。
采用本技术方案,催化剂在合成预聚体中占0.01-0.05%。
优选的,所述亲水扩链剂为二羟甲基丙酸、二羟甲基丁酸中的一种或多种。
采用本技术方案,亲水扩链剂在合成预聚体中占3.3%-4.5%。
优选的,所述中和剂为三乙胺或N,N-二甲基乙醇胺。
采用本技术方案,中和度为90%-100%。
优选的,所述后扩链剂为水合肼、乙二胺、异佛二酮二胺中的一种。
采用本技术方案,所述后扩链剂的加入量为体系中残余异氰酸酯的摩尔比为0.2-0.4:1。
为实现上述目的,本发明提供如下技术方案:
一种可降解水性聚氨酯的制备方法,包括以下步骤:
(1)预聚:在干燥高纯氮气的保护下,将二异氰酸酯投入到含真空脱水的多元醇的四口烧瓶中,在催化剂的存在下反应制得预聚体,反应温度80-90℃,时间1-2h;降低反应体系的温度至50-70℃,加入小分子扩链剂和亲水性扩链剂及葡萄糖,同时向反应体系中加入适量丙酮以控制体系粘度,再升温至70-80℃,混合反应2-3h;
(2)乳化:将预聚体导入乳化釜中,加入适量三乙胺或二甲基乙醇胺作为中和剂,在高速剪切下加入去离子水乳化,最后加入后扩链剂分散均匀;
(3)真空脱除丙酮,即制得可降解水性聚氨酯。
与现有技术相比,本发明的有益效果是:
(1)本发明为一种可降解水性聚氨酯及其制备方法,本发明提供的可降解水性聚氨酯乳液,通过聚己内脂二醇与聚乳酸二醇复合使用提高了单纯使用聚乳酸聚氨酯材料难于成膜,拉伸强度较低的缺点;
(2)本发明为一种可降解水性聚氨酯及其制备方法,本发明采用葡萄糖作为交联剂,葡萄糖含有五个活性羟基,可提高水性聚氨酯的交联度,从而改善胶膜的耐水性和耐溶剂性;
(3)本发明为一种可降解水性聚氨酯及其制备方法,本发明的可降解水性聚氨酯工艺简单,且仅适用少量低沸点的丙酮做溶剂,易于脱除,不造成有机溶剂污染。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1
一种可降解水性聚氨酯的制备方法,包括以下步骤:
步骤一:将300g聚乳酸二醇和110g聚己内酯二醇加入到装有搅拌器,温度计的四口烧瓶中,加热至110℃,抽真空脱水,真空度显示-0.08Mpa,1.5h后降温至75℃以下,降真空管口换为冷凝回流管,投入103.00g异佛二酮二异氰酸酯,加二丁基二月硅酸锡0.09g,混匀后升温至85-90℃,反应2h;
步骤二:降低所得到的预聚体的温度至60℃,加入2.70g 1,6-己二醇、0.50g葡萄糖和18.2g二羟甲基丙酸,同时加入丙酮控制反应体系粘度,在70-75℃条件下,进行扩链反应,时间为3h,制得预聚体;
步骤三:将预聚体转入乳化釜中,加入13.60g三乙胺,高速剪切下加水乳化,水温为20-25℃,最后加入乙二胺10%水溶液18.83g分散均匀,真空脱除丙酮,即制得可降解水性聚氨酯的乳液。
所得乳液的固含量为43%,粘度为90mPa.s,pH值:7.35。
实施例2
一种可降解水性聚氨酯的制备方法,包括以下步骤:
步骤一:将187.50g聚乳酸二醇和62.5g聚己内酯二醇加入到装有搅拌器,温度计的四口烧瓶中,加热至120℃,抽真空脱水,真空度显示-0.09Mpa,1.5h后降温至75℃以下,降真空管口换为冷凝回流管,投入46.00g异佛二酮二异氰酸酯和42.00g二环己基甲烷二异氰酸酯,加辛酸亚锡0.09g,混匀后升温至85-90℃,反应2h;
步骤二:降低所得到的预聚体的温度至60℃,加入2.10g 1,4-丁二醇、0.4g葡萄糖和15.20g二羟甲基丙酸,同时加入丙酮控制反应体系粘度,在70-75℃条件下,进行扩链反应,时间为3h,制得预聚体;
步骤三:将预聚体转入乳化釜中,加入11.45g三乙胺,高速剪切下加水乳化,水温为20-25℃,最后加入乙二胺10%水溶液13.28g分散均匀,真空脱除丙酮,即制得可降解水性聚氨酯的乳液。
所得乳液的固含量为38%,粘度为90mPa.s,pH值:7.28。
实施例3
一种可降解水性聚氨酯的制备方法,包括以下步骤:
步骤一:将252g聚乳酸二醇和63g聚己内酯二醇加入到装有搅拌器,温度计的四口烧瓶中,加热至120℃,抽真空脱水,真空度显示-0.08Mpa,1.5h后降温至75℃以下,降真空管口换为冷凝回流管,投入99.00g异佛二酮二异氰酸酯,加辛酸亚锡0.08g,混匀后升温至80-85℃,反应1.5;
降低所得到的预聚体的温度至60℃,加入2.32g 1,6-己二醇、0.4g葡萄糖和15.00g二羟甲基丙酸,同时加入丙酮控制反应体系粘度,在70-75℃条件下,进行扩链反应,时间为2.5h,制得预聚体;
将预聚体转入乳化釜中,加入9.57g二甲基乙醇胺,高速剪切下加水乳化,水温为20-25℃,最后加入异佛二酮二胺10%水溶液35.31g分散均匀,真空脱除丙酮,即制得可降解水性聚氨酯的乳液。
所得乳液的固含量为38%,粘度为80mPa.s,pH值:7.27。
将实施例1-3所制得的可降解水性聚氨酯对PHA卡片进行涂布,所得到的卡片涂层在常温常压下进行物化性能测试,主要指标如表1:
表1可降解水性聚氨酯涂布PHA卡片后涂层分析测试主要指标
实施例1-3所制得的涂层卡片与其他聚氨酯涂层卡片采用OKIC711DN彩色打印机打印,对比结果如表2:
表2不同涂层卡片激光打印后的主要性能对比
采用土埋法测定实施例1-3涂层胶膜的生物降解效果:胶膜埋入土中,微生物和水分子逐步侵蚀胶膜,使聚氨酯分子发生降解。实施例所制得的可降解水性聚氨酯和普通脂肪族水性聚氨酯、普通芳香族水性聚氨酯分别涂布到相同的PVC薄膜上,干基厚度均为16μm,与相同的200μm厚度的PVC卡片覆合,在同一台层压机上,设置温度为150℃,压力为4MPa进行层压。上述三种制备完成的卡片分别裁成50mm×50mm的标准试样,埋入深度为20cm的花园土壤中。层压即时剥离时间计时为0周,以后每隔一周取出一次对覆膜卡片进行剥离强度衰减测试,降解程度越大,剥离强度衰减相应越快。主要指标如表3:
表3土埋法测试实施例1-3胶膜生物降解主要指标
最后应说明的是:以上实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
Claims (10)
1.一种可降解水性聚氨酯,其特征在于,包括按重量份数计的如下组分:二异氰酸酯80-120份、多元醇240-480份、内交联剂0.1-0.8份、小分子扩链剂1-3份、催化剂0.01-0.1份、亲水扩链剂12-24份、中和剂11-16份和后扩链剂12-24份。
2.根据权利要求1所述的一种可降解水性聚氨酯,其特征在于,所述二异氰酸酯为异佛二酮二异氰酸酯、二环己基甲烷二异氰酸酯中的一种或多种。
3.根据权利要求1所述的一种可降解水性聚氨酯,其特征在于,所述多元醇为聚己内酯二醇和聚乳酸二醇的混合物。
4.根据权利要求1所述的一种可降解水性聚氨酯,其特征在于,所述内交联剂为葡萄糖。
5.根据权利要求1所述的一种可降解水性聚氨酯,其特征在于,所述小分子扩链剂为1,4-丁二醇、1,6-己二醇中的一种或多种。
6.根据权利要求1所述的一种可降解水性聚氨酯,其特征在于,所述催化剂为二丁基二月硅酸锡、辛酸亚锡中的一种。
7.根据权利要求1所述的一种可降解水性聚氨酯,其特征在于,所述亲水扩链剂为二羟甲基丙酸、二羟甲基丁酸中的一种或多种。
8.根据权利要求1所述的一种可降解水性聚氨酯,其特征在于,所述中和剂为三乙胺或N,N-二甲基乙醇胺。
9.根据权利要求1所述的一种可降解水性聚氨酯,其特征在于,所述后扩链剂为水合肼、乙二胺、异佛二酮二胺中的一种。
10.一种如权利要求1~9中任一项所述的可降解水性聚氨酯的制备方法,包括以下步骤:
(1)预聚:在干燥高纯氮气的保护下,将二异氰酸酯投入到含真空脱水的多元醇的四口烧瓶中,在催化剂的存在下反应制得预聚体,反应温度80-90℃,时间1-2h;降低反应体系的温度至50-70℃,加入小分子扩链剂和亲水性扩链剂及葡萄糖,同时向反应体系中加入适量丙酮以控制体系粘度,再升温至70-80℃,混合反应2-3h;
(2)乳化:将预聚体导入乳化釜中,加入适量三乙胺或二甲基乙醇胺作为中和剂,在高速剪切下加入去离子水乳化,最后加入后扩链剂分散均匀;
(3)真空脱除丙酮,即制得可降解水性聚氨酯。
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