CN117586471A - 一种具有荧光性能的自修复超疏水聚氨酯及其制备方法 - Google Patents
一种具有荧光性能的自修复超疏水聚氨酯及其制备方法 Download PDFInfo
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- CN117586471A CN117586471A CN202410071998.8A CN202410071998A CN117586471A CN 117586471 A CN117586471 A CN 117586471A CN 202410071998 A CN202410071998 A CN 202410071998A CN 117586471 A CN117586471 A CN 117586471A
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种具有荧光性能的自修复超疏水聚氨酯及其制备方法,属于自修复材料技术领域,所述聚氨酯是由二异氰酸酯、长链二醇、2,2‑二羟甲基丙酸、1,4‑丁二醇、氨基苯硼酸和三乙胺按照摩尔比1:0.3‑0.4:0.1‑0.3:0.3‑0.4:0.1‑0.3:0.1‑0.3反应得到。本发明所制备的材料含有可逆硼酸酯键,赋予了材料优异的自修复性能,自修复效率约为99.7%;通过在聚氨酯乳液中添加改性纳米二氧化硅,使聚氨酯涂层具备了超疏水性能,接触角最高达到171.6°;同时,由于胺基苯硼酸的引入,使材料具有优异的荧光性能。因此,本发明制备的多功能材料在超疏水涂层、防腐材料、防伪标识、感光材料等领域具有广阔的应用前景。
Description
技术领域
本发明属于自修复材料技术领域,特别涉及一种具有荧光性能的自修复超疏水聚氨酯及其制备方法。
背景技术
聚氨基甲酸酯,简称为聚氨酯(PU),PU结合了金属的耐用性、韧性与橡胶的弹性,现已得到大量应用。在聚氨酯主要链段上引入亲水基团而使聚氨酯可以成为聚氨酯乳液,聚氨酯乳液不仅具备一定的稳定性和环保特性,还具备良好的耐磨性、耐低温性、耐化学性和机械性能。但此类聚氨酯中存在亲水基团,不仅导致其耐水性较差还在使用过程容易受到外部刺激,使其内部形成裂纹,而这种损伤将对其性能产生负面影响,降低材料的使用寿命。因此,研究兼具超疏水特性、自修复特性的水性类聚氨酯涂层,对于提高材料的耐水性、延长材料的使用寿命有至关重要的意义。
已经报道的水性聚氨酯涂层,主要是通过向聚氨酯乳液的分子结构上引入可逆的共价键(二硫键、亚胺键、DA反应、2 + 2环加成等)或非共价键(氢键,金属配位键,静电相互作用等),来实现涂层的自修复。硼酸酯键是由硼酸及其衍生物与1, 2-二醇、1, 3-二醇或邻苯二酚基团形成的可逆共价键。它包含一个硼原子和一个羟基共结合,它们共结合时,硼原子的8个电子会包围羟基的一对电子,从而使其高度耦合,因此使得硼酸酯结构高度稳定。通过调节水溶液的pH值可以实现硼酸-二醇/二酚和硼酸酯键的相互转化,因此硼酸酯键常被引入聚合物或水凝胶实现材料的自修复性能。硼酸脱水缩合生成的硼氧六环具有比硼酸酯更高的官能度,在理论上会具有比含有相同数量的硼酸酯交联材料更高的交联密度和力学强度,所以在制备自修复高强度材料方面会具有独特的优势。
本发明在制备聚氨酯乳液过程中,引入了胺基苯硼酸结构进行封端,通过苯硼酸结构脱水缩合生成可逆的硼氧六元环结构,最终赋予了聚氨酯涂层优异的自修复性能,在70℃下修复3h后,自修复效率可以达到99.7%;室温下自修复效率为86.7%,与基于硼酸酯结构的水性聚氨酯(DOI:10.27242/d.cnki.gnjlu.2023.000814.)相比(60℃修复24h,修复效率83%),修复效率明显提高。通过向合成的聚氨酯乳液中引入改性的纳米二氧化硅,使涂层具有优异的超疏水性能(疏水角为169.6°,滚动角为1.3°)。除此之外,由于氨基苯硼酸的引入,赋予了聚氨酯优异的簇聚诱导发光性能,在365nm紫外光照射下,乳液显示出明亮的蓝色荧光,当移开紫外光后,材料有短时间的余晖。因此,本发明制备的聚氨酯在防伪涂层或薄膜、防腐涂层、感光材料等领域具有广阔的应用前景。
发明内容
本发明是针对现有自修复水性聚氨酯耐水性差,自修复效率低的缺点,提供一种修复效率高、具有高耐水性和超疏水性能的聚氨酯涂层。
本发明的另一个目的是解决现有自修复涂层功能单一的难题,通过向聚氨酯乳液中引入氨基苯硼酸,赋予材料优异的荧光性能,在防伪涂层领域,具有广阔的应用前景。
为了达到上述目的,本发明采用以下技术方案予以实现:
本发明提供的具有荧光性能的自修复超疏水聚氨酯是由二异氰酸酯、长链二醇、2, 2-二羟甲基丙酸、1, 4-丁二醇、氨基苯硼酸和三乙胺按照摩尔比1:0.3-0.4:0.1-0.3:0.3-0.4:0.1-0.3:0.1-0.3反应得到。
所述的二异氰酸酯为4, 4′-二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、4, 4′-二苯甲烷二异氰酸酯、甲苯-2, 4-二异氰酸酯中的一种或多种。
所述的长链二醇为分子量1000-4000的聚硅氧烷二醇、聚四氢呋喃二醇、聚丙二醇、聚乙二醇中的一种或多种。
所述氨基苯硼酸为2-氨基苯硼酸、3-氨基苯硼酸和4-氨基苯硼酸中的一种或多种。
所述的具有荧光性能的自修复超疏水聚氨酯的制备方法,包括如下步骤:
S1、聚氨酯乳液的制备:在氮气保护下,将二异氰酸酯、长链二醇、2, 2-二羟甲基丙酸加入到装有搅拌器、玻璃瓶塞的三口烧瓶中,均匀混合后加入二月桂酸二丁锡作为催化剂,反应2-3小时;加入1, 4丁二醇后反应2-3小时,期间加入丙酮降粘;冷却到0℃后,用滴液漏斗滴加含氨基苯硼酸的丙酮溶液,并继续搅拌1-2小时;升温到40℃后,加入三乙胺,搅拌30min后加入去离子水,经2000 rpm高速分散40min后得到聚氨酯乳液;二异氰酸酯、长链二醇、2, 2-二羟甲基丙酸、1, 4-丁二醇、氨基苯硼酸和三乙胺按照摩尔比为1:0.3-0.4:0.1-0.3:0.3-0.4:0.1-0.3:0.1-0.3添加;
S2、具有荧光性能的自修复超疏水聚氨酯的制备:将聚氨酯乳液、改性纳米二氧化硅和无水乙醇按质量比1:0.3-1.2:3混合,利用喷枪在基体上喷涂混合溶液,经室温干燥,得到具有荧光性能的自修复超疏水聚氨酯。
与现有技术相比,本发明的有益之处在于:
其一、本发明向聚氨酯乳液中引入氨基苯硼酸进行封端,通过苯硼酸脱水缩合形成的可逆硼氧六环结构,实现了聚氨酯涂层的自修复性能。与现有基于硼酸酯结构的自修复水性聚氨酯相比,修复效率有明显提升。
其二、本发明通过向聚氨酯乳液中引入氨基苯硼酸结构,赋予了聚氨酯优异的荧光性能,在防伪涂料和防伪薄膜领域具有广阔的应用前景。
其三、本发明通过向聚氨酯乳液中加入一定量的改性纳米二氧化硅,使得聚氨酯涂层具有优异的超疏水性能,进一步提高了涂层的耐水性能。
本发明的其它优点、目标和特征将部分通过下面的说明体现,部分还将通过对本发明的研究和实践而为本领域的技术人员所理解。
附图说明
图1.实施案例1的聚氨酯薄膜的红外光谱图;
图2.图1中灰色标注部分红外光谱放大图;
图3.实施案例1的聚氨酯乳液的贮存稳定性测试图;
图4.实施案例1的聚氨酯薄膜的拉伸性能及自愈合性能测试图;
图5.实施案例1的聚氨酯薄膜的自愈合过程图;
图6.实施案例1的聚氨酯薄膜的自愈合显微镜放大图;
图7.实施案例1的聚氨酯乳液的荧光光谱测试图;
图8.实施案例1的聚氨酯乳液的荧光观察图;
图9.实施案例1的聚氨酯接触角测试图,其中图9A为聚氨酯薄膜接触角测试图,图9B为具有荧光性能的自修复超疏水聚氨酯接触角测试图;
图10.实施案例1的具有荧光性能的自修复超疏水聚氨酯的滚动角测试图;
图11.实施案例2的聚氨酯薄膜的拉伸性能及室温自愈合性能测试图;
图12.实施案例2的具有荧光性能的自修复超疏水聚氨酯的接触角测试图;
图13.实施案例3的聚氨酯薄膜的拉伸性能及自愈合性能测试图;
图14.实施案例3的具有荧光性能的自修复超疏水聚氨酯的接触角测试图;
图15.实施案例4的具有荧光性能的自修复超疏水聚氨酯的接触角测试图。
具体实施方式
以下结合附图对本发明的优选实施案例进行说明,应当理解,此处所描述的优选实施案例仅用于说明和解释本发明,并不用于限定本发明。
实施案例1:
一种具有荧光性能的自修复超疏水聚氨酯及其制备方法,包括如下步骤:
(1)改性纳米二氧化硅的制备
利用氨水配制pH为10-11的碱性溶液30 mL,向氨水溶液中加入5 g纳米二氧化硅纳米颗粒粉末并磁力搅拌10min,制得A溶液;将0.5 mL全氟癸基三乙氧基硅烷(PFDTES)滴加到50 mL无水乙醇溶液中,室温下磁力搅拌60min,完成后制得B溶液;将A溶液缓慢加入到B溶液中在水浴温度50°C下磁力搅拌12h,反应完成后的产物在离心速度为10000 rpm下离心5min,无水乙醇清洗后在60℃下干燥24h,所得产物为改性纳米二氧化硅;
(2)聚氨酯乳液的制备
将4.5 g异佛尔酮二异氰酸酯、1.7 g羟丙基硅油、0.6 g2, 2-二羟甲基丙酸和5.2g聚四氢呋喃加入到装有搅拌器、玻璃瓶塞的三口烧瓶中,均匀混合;加入15 μL二月桂酸二丁锡后,在氮气气氛下用电热恒温水浴锅加热,升温至80℃反应2h后,将0.6 mL 1, 4丁二醇加入到聚氨酯预聚体中,于60℃下反应2h后加入含0.7 g 3-氨基苯硼酸的丙酮溶液,在冰浴下反应1h;向混合溶液中加入0.6 mL三乙胺,于40℃下反应30min;向成盐后的聚氨酯溶液中加入31.7 g去离子水,经高速分散机在2000 rpm分散40min后得到聚氨酯乳液;在聚四氟乙烯模具中于室温下静置72h,最后于55℃鼓风箱中干燥48h后可得到聚氨酯薄膜。反应方程式如下:
;
(3)具有荧光性能的自修复超疏水聚氨酯的制备
将聚氨酯乳液、改性纳米二氧化硅和无水乙醇按质量比1:0.8:3混合,利用喷枪在基体上喷涂混合溶液,经室温干燥,得到具有荧光性能的自修复超疏水聚氨酯;
图1为实施案例1的聚氨酯薄膜的红外光谱图 (KBr,cm-1),图2为图1中灰色标注部分红外光谱放大图,由此可看出在波数约3330 cm-1和1090 cm-1处形成的宽峰归属于氨基甲酸酯基团 (-NH(CO)O-) 和脲基 (-NHCONH-) 上N-H键的特征吸收峰,波数2950 cm-1和2860 cm-1处的峰分别为甲基和亚甲基的反对称吸收峰和对称吸收峰,1700 cm-1处所对应的峰归属于氨基甲酸酯基团上的C=O的伸缩振动峰,波数约708 cm-1处所对应的特征吸收峰为B3O3基团的伸缩振动峰;
图3为实施案例1的聚氨酯乳液的贮存稳定性测试图,步骤(2)的聚氨酯乳液在测试条件为3000 rpm下离心加速沉降试验30min模拟贮存稳定性,结果显示经离心后聚氨酯乳液无沉降现象,表明至少有6个月的贮存稳定期;
图4为实施案例1的聚氨酯薄膜的拉伸性能及自愈合性能测试图,自愈合性能的测试方法是将完整的聚合物样品切成两半,将断裂面用水和乙醇5:1的混合物浸泡1min,然后用外力使断裂面接触,在70℃下放置3小时后使用500N的万能试验机对修复后的样品以50mm/min的拉伸速率进行拉伸测试。自修复效率定义为修复后样品的拉伸强度与原始样品的拉伸强度之比。测试结果显示,在添加25% 3-氨基苯硼酸后,经硼氧六环的作用,聚氨酯拉伸强度为4.3 MPa,自修复效率高达99.7%,且断裂伸长率的修复效率也达到96.7%;
图5为实施案例1的聚氨酯薄膜的自愈合过程图,将聚氨酯薄膜切成两半,断裂面用水和乙醇5:1的混合物浸泡1 min后,用外力使两个湿润的断裂面接触,在70℃下放置3小时。结果显示,在70℃条件下修复3小时后,聚合物样品的断裂面消失,且几乎看不见剪切造成的损伤,表现出良好的自修复性能,且自修复后的聚合物可承受至少500 g重量的砝码;
图6为实施案例1的聚氨酯薄膜的自愈合显微镜放大图,从图中可以看到使用手术刀在聚氨酯薄膜上划出的裂纹经70℃下热处理5min后放大100倍观察发现部***纹明显变窄,部***痕已经消失;
图7为实施案例1的聚氨酯乳液的荧光光谱测试图,将聚氨酯乳液固含量调整为0.5%,选用日立 F-7000 DC-0506荧光光谱仪,狭缝2.5 nm,激发波长280 nm。图中观察可以得到发射光谱显示为宽带发射,发射主峰的位置在325-350 nm之间以及400-500 nm之间,属于簇聚诱导发光发光范围;
图8为实施案例1的聚氨酯乳液的荧光观察图,图中显示,添加了25% 3-氨基苯硼酸的聚氨酯荧光乳液在太阳光与黑暗条件下均不发光,但在365 nm点光源的照射下发光性能良好,有乳液的部分发光均匀;
图9为实施案例1的聚氨酯接触角测试图,其中图9A为聚氨酯薄膜接触角测试图,图9B为具有荧光性能的自修复超疏水聚氨酯接触角测试图。图9A显示经步骤(2)制备的聚氨酯薄膜接触角为70.4°;由图9B可以看到经步骤(3)制备的具有荧光性能的自修复超疏水聚氨酯接触角为169.6°。聚氨酯疏水性得到大幅度提升;
图10为实施案例1的具有荧光性能的自修复超疏水聚氨酯滚动角测试图,图中显示,经步骤(3)制备的具有荧光性能的自修复超疏水聚氨酯滚动角为1.3°,完全具备超疏水效果。
实施案例2:
一种具有荧光性能的自修复超疏水聚氨酯及其制备方法,包括如下步骤:
(1)改性纳米二氧化硅的制备方法同实施案例1中的步骤(1)
(2)聚氨酯乳液的制备
将6.92 g4, 4’-二苯甲烷二异氰酸酯、1.68 g六亚甲基二异氰酸酯、1.7 g羟丙基硅油、0.6 g2, 2-二羟甲基丙酸和5.2 g聚丙二醇加入到装有搅拌器、玻璃瓶塞的三口烧瓶中,均匀混合;加入15 μL二月桂酸二丁锡后,在氮气气氛下用电热恒温水浴锅加热,升温至80℃后反应2h;将0.6 mL1, 4丁二醇加入到聚氨酯预聚体中,于60℃下反应2h,期间加入丙酮降粘;用恒压漏斗滴加含0.7 g2-氨基苯硼酸的丙酮溶液,于冰浴下反应1h;向混合溶液中加入0.6 mL三乙胺,在40℃下反应30min;向成盐后的聚氨酯溶液中加入33.2 g去离子水,经高速分散机在2000 rpm分散40min后得到聚氨酯乳液,在聚四氟乙烯模具中于室温下静置72h,最后于55℃鼓风箱中干燥48h后可得到聚氨酯薄膜。反应方程式如下:
;
(3)具有荧光性能的自修复超疏水聚氨酯的制备
将聚氨酯乳液、改性纳米二氧化硅和无水乙醇按质量比1:1:3混合后,利用喷枪在基体上喷涂混合溶液,经室温干燥,得到具有荧光性能的自修复超疏水聚氨酯;
图11为实施案例2的聚氨酯薄膜的拉伸性能及室温自愈合性能测试图,室温自愈合性能的测试方法是将完整的聚合物样品切成两半,将断裂面用水和乙醇5:1的混合物浸泡1min,然后用外力使断裂面接触,在室温下放置48小时后使用500N的万能试验机对修复后的样品以50 mm/min的拉伸速率进行拉伸测试。自修复效率定义为修复后样品的拉伸强度与原始样品的拉伸强度之比。测试结果显示,在添加25% 2-氨基苯硼酸后,聚氨酯拉伸强度为6.1MPa,经室温修复后,自修复效率达到87.6%;
图12为实施案例2的具有荧光性能的自修复超疏水聚氨酯的接触角测试图,由图可以看出接触角为162.9°。
实施案例3:
一种具有荧光性能的自修复超疏水聚氨酯的制备方法,包括如下步骤:
(1)改性纳米二氧化硅的制备方法同实施案例1中的步骤(1)
(2)聚氨酯乳液的制备
将5.24 g4, 4′-二环己基甲烷二异氰酸酯、1.7 g羟丙基硅油、0.6 g2, 2-二羟甲基丙酸和5.2 g聚乙二醇加入到装有搅拌器、玻璃瓶塞的三口烧瓶中,均匀混合;加入15 μL二月桂酸二丁锡后,在氮气气氛下用电热恒温水浴锅加热,升温至80℃后反应2h;将0.6mL1, 4丁二醇加入到聚氨酯预聚体中,于60℃下反应2h,期间加入丙酮降粘;用恒压漏斗逐步滴加含0.7 g4-氨基苯硼酸的丙酮溶液,于冰浴下反应1h;向混合溶液中加入0.6 mL三乙胺,于40℃下反应30min;向成盐后的聚氨酯溶液中加入31.2 g去离子水,经高速分散机在2000 rpm分散40min后得到聚氨酯乳液,在聚四氟乙烯模具中于室温下静置72h,最后于55℃鼓风箱中干燥48h后可得到聚氨酯薄膜。反应方程式如下:
;
(3)具有荧光性能的自修复超疏水聚氨酯的制备方法同实施案例2中的步骤(3)
图13为实施案例3的聚氨酯薄膜的拉伸性能及自愈合性能测试图,测试结果显示,聚氨酯初始拉伸强度为10.5 MPa,自修复效率为87.6%;
图14为实施案例3的具有荧光性能的自修复超疏水聚氨酯的接触角测试图,由图可以看出接触角为171.6°。
实施案例4:
一种具有荧光性能的自修复超疏水聚氨酯的制备方法,包括如下步骤:
(1)改性纳米二氧化硅的制备方法同实施案例1中的步骤(1)
(2)聚氨酯乳液的制备
将3.48 g甲苯-2, 4-二异氰酸酯、1.7 g羟丙基硅油、0.6 g 2, 2-二羟甲基丙酸和5.2 g聚四氢呋喃加入到装有搅拌器、玻璃瓶塞的三口烧瓶中,均匀混合;加入15 μL二月桂酸二丁锡后,在氮气气氛下用电热恒温水浴锅加热,升温至80℃后反应2h;将0.6mL 1, 4丁二醇加入到聚氨酯预聚体中,于60℃下反应2h,期间加入丙酮降粘;用恒压漏斗逐步滴加含0.7 g4-氨基苯硼酸的丙酮溶液,于冰浴下反应1h;向混合溶液中加入0.6 mL三乙胺,于40℃下反应30min;向成盐后的聚氨酯溶液中加入31.2 g去离子水,经高速分散机在2000rpm分散40min后得到聚氨酯乳液,在聚四氟乙烯模具中于室温下静置72h,最后于55℃鼓风箱中干燥48h后可得到聚氨酯薄膜。反应方程式如下:
;
(3)具有荧光性能的自修复超疏水聚氨酯的制备方法同实施案例2中的步骤(3)
图15为实施案例4的具有荧光性能的自修复超疏水聚氨酯的接触角测试图,由图可以看出接触角为169.3°。
综上所述,本发明通过在聚氨酯乳液中引入足够多的硼氧六环结构,使聚氨酯薄膜在室温下自修复效率达到86.7%;加热条件下自修复效率提升到了99.7%,修复时间缩短为3h,同时制备的聚氨酯乳液和改性纳米二氧化硅共混喷涂还可以达到超疏水效果,完全避免了环境水对材料力学性能的影响,并且引入硼氧六环结构还使聚氨酯薄膜表现出发光行为,大大拓展了材料的应用范围,使材料适用于发光涂料、柔性器件、发光印刷、防腐材料、防伪标识、疏水涂层等多种领域。
以上所述,仅是本发明的较佳实施案例而已,并非对本发明作任何形式上的限制,虽然本发明已以较佳实施案例揭露如上,然而并非用以限定本发明,任何熟悉本专业的技术人员,在不脱离本发明技术方案范围内,当可利用上述揭示的技术内容作出些许更动或修饰为等同变化的等效实施案例,但凡是未脱离本发明技术方案的内容,依据本发明的技术实质对以上实施案例所作的任何简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。
Claims (5)
1.一种具有荧光性能的自修复超疏水聚氨酯,其特征在于,所述聚氨酯是由二异氰酸酯、长链二醇、2, 2-二羟甲基丙酸、1, 4-丁二醇、氨基苯硼酸和三乙胺按照摩尔比1:0.3-0.4:0.1-0.3:0.3-0.4:0.1-0.3:0.1-0.3反应得到,其结构通式为:
;
式中,R1为下述结构式中的一种或多种:
;
式中,R2为下述结构式中的一种或多种:
;
其中,m的取值范围为11-91,
式中,R3为下述结构式中的一种或多种:
。
2.如权利要求1所述的具有荧光性能的自修复超疏水聚氨酯,其特征在于,所述的二异氰酸酯为4, 4′-二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、4,4′-二苯甲烷二异氰酸酯、甲苯-2, 4-,二异氰酸酯中的一种或多种。
3.如权利要求1所述的具有荧光性能的自修复超疏水聚氨酯,其特征在于,所述的长链二醇为分子量1000-4000的聚硅氧烷二醇、聚四氢呋喃二醇、聚丙二醇、聚乙二醇中的一种或多种。
4.如权利要求1所述的具有荧光性能的自修复超疏水聚氨酯,其特征在于,所述氨基苯硼酸为2-氨基苯硼酸、3-氨基苯硼酸和4-氨基苯硼酸中的一种或多种。
5.如权利要求1- 4任一项所述的具有荧光性能的自修复超疏水聚氨酯的制备方法,其特征在于,包括如下步骤:
S1、聚氨酯乳液的制备:在氮气保护下,将二异氰酸酯、长链二醇、2, 2-二羟甲基丙酸加入到装有搅拌器、玻璃瓶塞的三口烧瓶中,均匀混合后加入二月桂酸二丁锡作为催化剂,反应2-3小时;加入1, 4丁二醇后反应2-3小时,期间加入丙酮降粘;冷却到0℃后,用滴液漏斗滴加含氨基苯硼酸的丙酮溶液,并继续搅拌1-2小时;升温到40℃后,加入三乙胺,搅拌30min后加入去离子水,经2000 rpm高速分散40min后得到聚氨酯乳液;二异氰酸酯、长链二醇、2, 2-二羟甲基丙酸、1, 4-丁二醇、氨基苯硼酸和三乙胺按照摩尔比为1:0.3-0.4:0.1-0.3:0.3-0.4:0.1-0.3:0.1-0.3添加;
S2、具有荧光性能的自修复超疏水聚氨酯的制备:将聚氨酯乳液、改性纳米二氧化硅和无水乙醇按质量比1:0.3-1.2:3混合,利用喷枪在基体上喷涂混合溶液,经室温干燥,得到具有荧光性能的自修复超疏水聚氨酯。
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