CN105924604B - 一种可降解水性聚氨酯涂料的制备方法及产品 - Google Patents
一种可降解水性聚氨酯涂料的制备方法及产品 Download PDFInfo
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Abstract
本发明公开了一种制备可降解水性聚氨酯涂料的方法,通过纳米二氧化钛对水性聚氨酯进行改性,纳米二氧化钛颗粒具有的表面与界面效应、量子尺寸效应和宏观量子隧道效应等特殊性质,能够改善水性聚氨酯耐水性以及机械力学性等,同时纳米二氧化钛自身的抗菌性能有效减少微生物在涂层表面的附着,又通过在纳米二氧化钛表面连接聚乳酸,制备具有可降解性的水性聚氨酯涂料。本发明利用甲苯二异氰酸酯官能团‑NCO的连接作用,制备端基为‑NCO来连接二氧化钛/聚乳酸复合涂料,达到改性水性聚氨酯的目的,聚乳酸主链柔软,易被自然界中的微生物分解代谢,且分解产物无污染,有效的将附着在表面的微生物清除下来;纳米二氧化钛具有抗菌杀菌的优良特性,大大减少污损生物的附着,保持涂层表面清洁。
Description
技术领域
本发明属于高分子纳米复合材料领域,涉及一种可降解水性聚氨酯涂料的制备方法。
技术背景:
在人类对海洋资源开发及利用的进程中,海洋污损生物成为阻碍海洋经济发展的一大难题。此类生物一旦在船底附着,将会导致船舶航行速度减慢,增大阻力,浪费燃料;腐蚀金属表面涂层,加速金属老化,降低船舶使用寿命;处理在船舶表面的附着物消耗大量的人力物力,造成巨大经济损失;此外,一旦随船舶进入新的海洋领域,造成外来物种入侵,对海洋生态系统造成破坏。因此,解决海洋污损生物带来的困扰迫在眉睫。
迄今为止,人类采用的最普遍经济有效的防污方法是设备表面喷涂海洋防污涂料。传统海洋防污涂料中的有机锡类毒性分子化合物会对海洋生物造成严重危害,国际海事组织规定自2008年起禁用有机锡化合物。新型环保海洋防污涂料的开发成为迫切需要解决的问题。20世纪末,有机硅海洋防污涂料得到快速发展,目前已形成商品化产品,纯有机硅海洋防污涂料的防污作用机理是通过硅油或其它助剂从涂层本体渗到表面,使污损物附着在油面上更易脱落,从而起到防污作用。然而这些产品虽然性能优异,但与传统的防污涂料相比防污效果稍差且价格更高。此类涂料的缺点也很明显,突出问题是较短时间内会释放完硅油或其它助剂,涂层失去防污性能;且这种涂层的重涂性也差,不易进行修补。(秦瑞瑞,胡生祥,宫祥怡.有机硅低表面能海洋防污涂料的研究进程[J].2015, 29(1):74 ~77)有机硅海洋防污涂料仍有很多问题亟待解决。因此,新型环保可降解型防污涂料成为行业研究热点。
水性聚氨酯具有高强度、高硬度、优异的耐疲劳性能和良好的柔韧性等优良的机械性能、同时以水代替有机溶剂作为分散介质,环保无污染且易被改性。根据其优良的性能,我们将水性聚氨酯用作具有特殊功能的功能性涂料。相比于溶剂型聚氨酯,水性聚氨酯引入了亲水性基团,使水性聚氨酯的耐水性等受到影响,水性聚氨酯涂层的耐候性、力学性能及防菌性等成为影响涂层性能的主要因素。因此,对水性聚氨酯进行改性将大大推动其在涂料上的应用。本发明中,利用纳米材料对其进行改性,制备具有可降解功能的水性聚氨酯涂料。
随着纳米技术的发展,纳米材料应用于各个领域,然而在船舶涂料方面应用并不广泛。而纳米材料颗粒尺寸小,其特有的表面与界面效应、量子尺寸效应和宏观量子隧道效应等特殊性质,能够改善水性聚氨酯耐水性以及机械力学性等。荧光防污涂层作为一种新型防污技术,根据海洋中的厌光生物趋向于远离夜间发光的物的性质,从而达到防污的目的。(刘丽萍,曾秀凤.环境友好型海洋防污涂层的研究进展[J].材料导报,2014.5,第28卷专辑23)国内学者,曾将纳米二氧化钛作为荧光物质加入涂层研究其对海洋生物附着量的影响。(齐育红,张占平.Nano-TiO2/FEVE氟碳涂层的水云藻附着性能[J].中国表面工程,2010, 23(2):74)同时,纳米二氧化钛具有抗菌杀菌作用,可用于抗菌防污涂料中,制备性能优良的自清洁涂层涂料。
发明内容:
本发明针对现有技术不足,提供一种新型环保可降解水性聚氨酯的制备方法,以可分解脱落的聚乳酸软链及具有杀菌作用的纳米二氧化钛颗粒来有效减少海洋污损生物在船体的附着。
为实现上述目的,本发明采用的技术方案为:一种可降解水性聚氨酯的制备方法,包括以下步骤:
(1)将纳米二氧化钛和丙交酯溶解在无水甲苯中,在110~130℃恒温搅拌条件下持续反应8-12 h,冷却到室温,将溶液滴加到8倍体积的正己烷中,不断搅拌,静置减压过滤得到二氧化钛/聚乳酸复合材料,将产物置于50℃真空干燥箱干燥12 h待用。
(2)将甲苯二异氰酸酯、聚丙二醇及2,2—二羟基甲基丙酸在70-80℃恒温搅拌的条件下持续反应10-14 h,冷却到40℃之后加入丙酮溶剂,降低反应粘度;加三乙胺中和剂,在80℃反应5小时。
(3)将步骤(1)反应所得的产物,溶解在四氢呋喃中,加入步骤(2)反应所得产物在恒温80~110℃下,反应6~10 h,结束反应后,待温度降到室温,将溶液滴加到8倍体积的正己烷中,不断搅拌,静置减压过滤,获得表面连接聚乳酸的可降解水性聚氨酯材料。
步骤(1)中所述的纳米二氧化钛,经过真空干燥过夜处理;所述的无水甲苯为新制金属钠除水甲苯;所述的丙交酯的开环聚合成聚乳酸采用了辛酸亚锡做催化剂;二氧化钛分散到无水甲苯中后,通过超声波处理使其充分混合。
步骤(2)中所用聚丙二醇为在真空条件下脱水所得;所用的2,2—二羟基甲基丙酸为在真空条件下干燥所得。
步骤(2)中水性聚氨酯采用以下重量比原料制成:聚丙二醇10-15份、甲苯二异氰酸酯1-4份及2,2—二羟基甲基丙酸1-2份。
步骤(1)、(2)制备所得产物应在24 h之内进行步骤(3)反应。
步骤(3)中的四氢呋喃经过新制金属钠除水处理。
步骤(3)所用的步骤(2)和步骤(1)的产物的质量之比为1-3:1。
一种根据所述的方法制备的可降解水性聚氨酯涂料。
本发明的有益效果:本发明利用甲苯二异氰酸酯官能团-NCO的连接作用,制备端基为-NCO来连接二氧化钛/聚乳酸复合材料,达到改性水性聚氨酯的目的,聚乳酸主链柔软,易被自然界中的微生物分解代谢,且分解产物无污染,有效的将附着在表面的微生物清除下来;纳米二氧化钛具有抗菌杀菌的优良特性,大大减少污损生物的附着,保持涂层表面清洁。且本发明所用原材料廉价,工艺简易,操作方便,为其工业化生产减少了成本,降低了难度。
原理及实验结果分析:
(1)如图1所示,纳米二氧化钛表面羟基引发丙交酯开环聚合成聚乳酸。聚酯键易水解,而主链柔软,易被自然界中的微生物分解代谢,聚乳酸最后变成二氧化碳和水,无污染。然后将连接有聚乳酸的纳米二氧化钛与制备的端基为-NCO的水性聚氨酯化合,反应如图2所示。纳米二氧化钛表面的聚乳酸被微生物分解,从分子链中断裂,脱离涂层,在水流的冲刷下,使附着在表面的微生物也随之脱离船舶表面,因此,可降解性水性聚氨酯具有抗微生物污损的特性。同时纳米二氧化钛本身具有抗菌杀菌作用,可以有效的抑制微生物的繁殖,大大减少了海洋污损生物的附着。
(2)如图3所示,a,b分别表示PLLA/TiO2及TiO2的红外光谱图。其中,在b曲线中,3430 cm-1处为纳米二氧化钛表面的O-H的伸缩振动吸收峰,1088 cm-1处为Ti-O的伸缩吸收峰;在a处,3500cm-1为PLLA/TiO2中O-H的伸缩振动吸收峰,2940cm-1及1460cm-1分别为C- H的伸缩振动吸收峰和弯曲振动吸收峰,在1750cm-1处为C=O的伸缩振动吸收峰,在1100 cm-1处为C-O的伸缩振动吸收峰。从以上峰值分析接枝产物中含有C=O化学键,说明丙交酯单体已经聚合,只形成聚乳酸,或开环与纳米二氧化钛表面的羟基反应连接在其表面。通过聚乳酸的溶解性能可知,聚乳酸溶于四氢呋喃,产物经四氢呋喃溶解后仍存在C=O及C-H键,故而可证得二氧化钛表面的羟基成功引了发LLA开环聚合并连接在纳米二氧化钛表面。
(3)如图4所示,a,b分别表示WPU及PLLA/TiO2/WPU的红外光谱图。其中,在a曲线中,在3291 cm-1及1602 cm-1处分别为N-H的伸缩振动吸收峰及弯曲振动吸收峰,在1724 cm-1处为C=O的伸缩振动吸收峰,在2262 cm-1处为-NCO的伸缩振动吸收峰,从以上峰值得,步骤二产物中含有明显的C=O与N-H,即形成了-NHCO-基团,又因为-NCO 的存在,说明成功合成端基团为-NCO的水性聚氨酯。
取部分步骤(2)产物加入适当的去离子水强力搅拌,如图5所示,a为搅拌前的情况,b为搅拌后的情况,经搅拌后能完全溶于水,证明制备的水性聚氨酯有良好的水溶性。在b曲线中,在2262 cm-1处为-NCO的伸缩振动吸收峰消失,在3439 cm-1处为-NH-的伸缩振动吸收峰,峰值明显增强,说明端基团为-NCO的水性聚氨酯加入PLLA/TiO2后成功化合,得到最终产物。
附图说明:
图1:丙交酯的开环聚合反应原理图;
图2:水性聚氨酯的制备原理图;
图3:PLLA/TiO2及TiO2的红外光谱图;
图4:WPU及PLLA/TiO2/WPU的红外光谱图;
图5:水性聚氨酯水溶情况示意图。
具体实施方式
实施例1:
将纳米二氧化钛50℃真空干燥24 h,将2.0 g纳米二氧化钛与50mL无水甲苯充分混合,超声波分散均匀,加入丙交酯0.5 g,迅速升温到125℃,加辛酸亚锡2mL做催化剂,在125℃氮气保护恒温搅拌的条件下反应12 h,纳米二氧化钛表面的羟基引发丙交酯开环,将反应得到的二氧化钛/聚乳酸复合材料及无水甲苯混合液滴加到8倍体积的正己烷中,减压过滤后,将产物50℃干燥待用。2,2-二羟基甲基丙酸在110℃除水,聚丙二醇在110℃进行脱水处理。将干燥好的聚丙二醇2.5 g和2,2—二羟基甲基丙酸0.3 g混合搅拌,缓慢滴加甲苯二异氰酸酯0.25 g,在氮气保护和强力搅拌条件下,75℃恒温反应8 h,降温到40℃之后加丙酮,降低反应黏度;加0.2 g三乙胺中和剂反应3 h,然后进行除丙酮处理,得到端基为-NCO的预聚物。将反应得到的二氧化钛/聚乳酸复合材料溶解在四氢呋喃溶液中,通过超声波混合均匀。与所得的水性聚氨酯在恒温90℃下,反应8 h,将溶液滴加到8倍体积的正己烷中,减压过滤,获得具有可降解性的水性聚氨酯产物。
实施例2:
将纳米二氧化钛50℃真空干燥24 h,将2.0 g纳米二氧化钛与50mL无水甲苯充分混合,超声波分散均匀,加入丙交酯1.0 g,迅速升温到125℃,加辛酸亚锡2mL做催化剂,在125℃氮气保护恒温搅拌的条件下反应12 h,纳米二氧化钛表面的羟基引发丙交酯开环,将反应得到的二氧化钛/聚乳酸复合材料及无水甲苯混合液滴加到8倍体积的正己烷中,减压过滤后,将产物50℃干燥待用。2,2-二羟基甲基丙酸在110℃除水,聚丙二醇在110℃进行脱水处理。将干燥好的聚丙二醇2.5 g和2,2—二羟基甲基丙酸0.3 g混合搅拌,缓慢滴加甲苯二异氰酸酯0.5 g,在氮气保护和强力搅拌条件下,75℃恒温反应10 h,降温到40℃之后加丙酮,降低反应黏度;加0.2 g三乙胺中和剂反应3 h,然后进行除丙酮处理,得到端基为-NCO的预聚物。将反应得到的二氧化钛/聚乳酸复合材料溶解在四氢呋喃溶液中,通过超声波混合均匀。与所得的水性聚氨酯在恒温90℃下,反应10 h,将溶液滴加到8倍体积的正己烷中,减压过滤,获得具有可降解性的水性聚氨酯产物。
实例3:
将纳米二氧化钛50℃真空干燥24 h,将2.0 g纳米二氧化钛与50mL无水甲苯充分混合,超声波分散均匀,加入丙交酯0.5 g,迅速升温到125℃,加辛酸亚锡2mL做催化剂,在125℃氮气保护恒温搅拌的条件下反应12 h,纳米二氧化钛表面的羟基引发丙交酯开环,将反应得到的二氧化钛/聚乳酸复合材料及无水甲苯混合液滴加到8倍体积的正己烷中,减压过滤后,将产物50℃干燥待用。2,2-二羟基甲基丙酸在110℃除水,聚丙二醇在110℃进行脱水处理。将干燥好的聚丙二醇5.0 g和2,2—二羟基甲基丙酸0.6 g混合搅拌,缓慢滴加甲苯二异氰酸酯0.5 g,在氮气保护和强力搅拌条件下,75℃恒温反应12 h,降温到40℃之后加丙酮,降低反应黏度;加0.4 g三乙胺中和剂反应3 h,然后进行除丙酮处理,得到端基为-NCO的预聚物。将反应得到的二氧化钛/聚乳酸复合材料溶解在四氢呋喃溶液中,通过超声波混合均匀。与所得的水性聚氨酯在恒温90℃下,反应8 h,将溶液滴加到8倍体积的正己烷中,减压过滤,获得具有可降解性的水性聚氨酯产物。
实例4:
将纳米二氧化钛50℃真空干燥24 h,将2.0 g纳米二氧化钛与50mL无水甲苯充分混合,超声波分散均匀,加入丙交酯0.5 g,迅速升温到125℃,加辛酸亚锡2mL做催化剂,在125℃氮气保护恒温搅拌的条件下反应12 h,纳米二氧化钛表面的羟基引发丙交酯开环,将反应得到的二氧化钛/聚乳酸复合材料及无水甲苯混合液滴加到8倍体积的正己烷中,减压过滤后,将产物50℃干燥待用。2,2-二羟基甲基丙酸在110℃除水,聚丙二醇在110℃进行脱水处理。将干燥好的聚丙二醇5.0 g和2,2—二羟基甲基丙酸0.6 g混合搅拌,缓慢分次滴加甲苯二异氰酸酯0.75 g,在氮气保护和强力搅拌条件下,75℃恒温反应14 h,降温到40℃之后加丙酮,降低反应黏度;加0.4 g三乙胺中和剂反应3 h,然后进行除丙酮处理,得到端基为-NCO的预聚物。将反应得到的二氧化钛/聚乳酸复合材料溶解在四氢呋喃溶液中,通过超声波混合均匀。与所得的水性聚氨酯在恒温90℃下,反应12 h,将溶液滴加到8倍体积的正己烷中,减压过滤,获得具有可降解性的水性聚氨酯产物。
上述实施例在以本发明技术方案为前提下进行实施,所给出的详细实施方式和过程,是对本发明的进一步说明,而不是限制本发明的范围。
Claims (8)
1.一种制备可降解水性聚氨酯涂料的方法,其特征在于,包括以下步骤:
(1)将纳米二氧化钛和丙交酯溶解在无水甲苯中,在110~130℃恒温搅拌条件下持续反应8-12 h,冷却到室温,将溶液滴加到8倍体积的正己烷中,不断搅拌,静置减压过滤得到二氧化钛/聚乳酸复合材料,将产物置于50℃真空干燥箱干燥12 h待用;
(2)将甲苯二异氰酸酯、聚丙二醇及2,2—二羟基甲基丙酸在70-80℃恒温搅拌的条件下持续反应10-14 h,冷却到40℃之后加入丙酮溶剂,降低反应粘度;加三乙胺中和剂,在80℃反应5-8 h;
(3)将步骤(1)反应所得的产物,溶解在四氢呋喃中,加入步骤(2)反应所得产物,在恒温80~110℃下,反应6~10 h,结束反应后,待温度降到室温,将溶液滴加到8倍体积的正己烷中,不断搅拌,静置减压过滤,获得表面连接聚乳酸的可降解水性聚氨酯涂料。
2.如权利要求1所述的一种制备可降解水性聚氨酯涂料的方法,其特征在于,步骤(1)中所述的纳米二氧化钛,经过真空干燥过夜处理;所述的无水甲苯为新制金属钠除水甲苯;所述的丙交酯的开环聚合成聚乳酸采用了辛酸亚锡做催化剂;二氧化钛分散到无水甲苯中后,通过超声波处理使其充分混合。
3.如权利要求1所述的一种制备可降解水性聚氨酯涂料的方法,其特征在于,步骤(2)中所用聚丙二醇为在真空条件下脱水所得;所用的2,2—二羟基甲基丙酸为在真空条件下干燥所得。
4.如权利要求1所述的一种制备可降解水性聚氨酯涂料的方法,其特征在于,步骤(2)中水性聚氨酯采用以下重量比原料制成:聚丙二醇10-15份、甲苯二异氰酸酯1-4份及2,2—二羟基甲基丙酸1-2份。
5.如权利要求1所述的一种制备可降解水性聚氨酯涂料的方法,其特征在于,步骤(1)、(2)制备所得产物应在24 h之内进行步骤(3)反应。
6.如权利要求1所述的一种制备可降解水性聚氨酯涂料的方法,其特征在于,步骤(3)中的四氢呋喃经过新制金属钠除水处理。
7.如权利要求1所述的一种制备可降解水性聚氨酯涂料的方法,其特征在于,步骤(3)所用的步骤(2)和步骤(1)的产物的质量之比为1-3:1 。
8.一种根据权利要求1-7任一项所述的方法制备的可降解水性聚氨酯涂料。
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