CN107163280A - 热处理后修饰法制备聚氨酯‑纳米银长效抗菌薄膜的方法 - Google Patents
热处理后修饰法制备聚氨酯‑纳米银长效抗菌薄膜的方法 Download PDFInfo
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- CN107163280A CN107163280A CN201710339632.4A CN201710339632A CN107163280A CN 107163280 A CN107163280 A CN 107163280A CN 201710339632 A CN201710339632 A CN 201710339632A CN 107163280 A CN107163280 A CN 107163280A
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Classifications
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Abstract
本发明涉及一种热处理后修饰法制备聚氨酯‑纳米银长效抗菌薄膜的方法，(1)将二异氰酸酯和聚四氢呋喃混合反应；加交联剂、扩链剂的丙酮溶液，加二羟甲基丙酸和催化剂反应，得PU；向聚氨酯溶液加硝酸银的二甲基甲酰胺溶液，搅匀后成膜，热处理，得聚氨酯‑纳米银薄膜；(2)将4,4′‑二羟基二苯甲酮与长链卤代烷反应，得4,4′‑双‑长链烷氧基二苯甲酮；4,4′‑双‑长链烷氧基二苯甲酮与水合肼反应得4,4′‑双‑长链烷氧基二苯甲酮腙；4,4′‑双‑长链烷氧基二苯甲酮腙经氧化反应得长链烷基重氮甲烷；(3)将长链烷基重氮甲烷溶于溶剂中，均匀涂覆到聚氨酯‑纳米银薄膜表面，热处理，即得。本发明能够实现长效抗菌。
Description
技术领域
本发明涉及热处理后修饰法制备聚氨酯-纳米银长效抗菌薄膜的方法，属于抗菌材料技术领域。
背景技术
聚氨酯是一类重要的医用高分子材料，具有优异的血液相容性、良好的生物稳定性和力学性能。傅强等(谭鸿,李洁华,傅强.生物医用磷脂化聚氨酯的设计、制备与性能.中国科学:化学,42(5),pp 661-675,2012.)研究表明，聚氨酯具有与天然血管最相匹配的顺应性，尤其适用于血液接触器件，在外科手术的治疗中具有不可替代的作用。但是，介入式医用高分子材料需具有长效抗菌性，否则临床应用时容易引起术后感染，导致手术和医疗事故。据美国国家卫生研究院初步统计，80％的细菌性疾病与医用材料有关。以心血管系统为例，人工装置感染导致的死亡率接近100％。因此，获得抗菌性好、抗菌期长的医用高分子材料，成为当今医学亟待解决的问题，也是化学、材料学、生物学等传统学科的交叉领域的研究热点。
近年来，纳米银材料的研究受到人们的广泛关注。银作为无机抗菌剂，具有久远的历史，其药用价值在古代的《本草纲目》中就有所记载。在最近的几十年里，抗菌剂尤其是纳米银的抗菌性能的研究大量增加，纳米银在生物医学中的应用也受到了极大的关注。纳米银可应用于纺织织物和伤口敷料、食品储存容器、导液管、绷带、饮用水消毒、家庭抗菌涂料和牙齿复合树脂等方面。它作为一种广谱性抗菌剂，对大肠杆菌、单核细胞李斯特菌、金黄色葡萄球菌等菌类具有高毒性，但对于动物细胞具有低毒性。
纳米银颗粒的尺寸在原子和宏观微粒之间，因此同时具备了纳米材料和单质银的优良特性，具有比表面积大、杀菌能力强等优点。当银的尺寸达到纳米级时，它会迅速在溶液中解离为Ag+，并发挥抗菌作用。目前，纳米银抗菌性聚氨酯材料的合成大都是先将聚氨酯材料合成，再将银纳米颗粒分散到聚氨酯材料中；但是，这种方法容易导致银纳米颗粒分散不均匀，容易团聚。
为了延长聚氨酯-纳米银材料的抗菌周期，人们也展开了广泛深入的研究。其中，疏水改性是使聚氨酯-纳米银材料实现长效抗菌活性的重要途径，改性后形成的疏水膜在纳米银颗粒与外界环境之间形成“软”屏障，因此能够延长其抗菌周期。目前，聚合物的疏水改性的研究主要依赖于特殊的化学反应，即首先获得具有特定功能基团的聚氨酯，然后在其表面实施易于发生的click反应，引入疏水性能基团进行改性。Fournier等人(FournierD,De Geest B G,Du Prez F E.On-demand click functionalization of polyurethanefilms and foams[J].Polymer,2009,50(23):5362-5367.)首先从比利时Recticel公司购买了表面功能化的聚氨酯海绵(表面基团为炔基)，然后用带有疏水烷基链的叠氮化合物与其进行1,3-偶极环加成反应，从而得到表面具有疏水性能的聚氨酯海绵材料。Nystrom等人(Nystrom D,Lindqvist J,Ostmark E,et al.Superhydrophobic and self-cleaningbio-fiber surfaces via ATRP and subsequent postfunctionalization[J].ACSapplied materials&interfaces,2009,1(4):816-823.)、Xu等人(Xu J,Boyer C.Visiblelight photocatalytic thiol–ene reaction:an elegant approach for fast polymerpostfunctionalization and step-growth polymerization[J].Macromolecules,2015,48(3):520-529.)也分别在购自Sigma-Aldrich公司的功能化纤维素、功能化聚丁二烯表面引入了疏水烷基链，达到提高疏水性的目的。然而，这种疏水改性方式均需要聚合物表面带有特殊的功能基团，而且，为了确保后续改性反应的顺利实施，这些功能基团(如炔基、烯基、叠氮等)的化学性质往往较为活泼、易于发生副反应而变质，导致这类聚合物的合成难度大，并不适用于普通的聚氨酯材料的表面改性。
发明内容
针对现有技术的不足，本发明提供一种热处理后修饰法制备聚氨酯-纳米银长效抗菌薄膜的方法。
本发明的技术方案如下：
一种热处理后修饰法制备聚氨酯-纳米银长效抗菌薄膜的方法，包括步骤如下：
(1)聚氨酯-纳米银薄膜的制备
将二异氰酸酯和聚四氢呋喃混合，于80-120℃反应1-10h；加入交联剂、扩链剂，再加入二羟甲基丙酸和催化剂，于60-90℃反应1-10h，得聚氨酯溶液(PU)；
向聚氨酯溶液中加入硝酸银的二甲基甲酰胺溶液，搅拌均匀后成膜，再进行热处理，即得聚氨酯-纳米银薄膜；
(2)长链烷基重氮甲烷的制备
将4,4′-二羟基二苯甲酮与长链卤代烷反应，得4,4′-双-长链烷氧基二苯甲酮；4,4′-双-长链烷氧基二苯甲酮与水合肼反应得4,4′-双-长链烷氧基二苯甲酮腙；4,4′-双-长链烷氧基二苯甲酮腙经氧化反应得长链烷基重氮甲烷；
(3)聚氨酯-纳米银长效抗菌薄膜的制备
将长链烷基重氮甲烷溶于溶剂中，均匀涂覆到聚氨酯-纳米银薄膜表面，于100-250℃热处理1-60min，即得聚氨酯-纳米银长效抗菌薄膜。
根据本发明，优选的，步骤(1)中所述的二异氰酸酯为4,4′-二环己基甲烷二异氰酸酯，所述的交联剂为三羟甲基丙烷，所述的扩链剂为1,6-己二醇，所述的催化剂为二月硅酸二丁基锡；
优选的，二异氰酸酯、聚四氢呋喃、交联剂、扩链剂、二羟甲基丙酸和催化剂的质量比为1：(0.8-1.2)：(0.01-0.1)：(0.1-1)：(0.01-0.1)：(0.001-0.01)；
优选的，交联剂和扩链剂分别溶于丙酮溶液中加入反应体系，交联剂和扩链剂的丙酮溶液中，交联剂或扩链剂的质量与丙酮的体积之比为1：(5-100)g/mL。
根据本发明，优选的，步骤(1)中硝酸银的加入量为聚氨酯溶液质量的1-20％，硝酸银的二甲基甲酰胺溶液中硝酸银的质量与二甲基甲酰胺的体积之比为1：(1-10)g/mL；
优选的，成膜后热处理的温度范围为25-200℃，热处理的时间为1-10h。
根据本发明，优选的，步骤(2)中所述的长链卤代烷为1-溴代十二烷；
优选的，4,4′-二羟基二苯甲酮与长链卤代烷的质量比为1：(2-20)；
优选的，反应温度为80-200℃，反应时间为10-100h；
4,4′-二羟基二苯甲酮与长链卤代烷反应后生成氯化氢，优选的，加入碳酸钾用于中和氯化氢，加快反应速率；4,4′-二羟基二苯甲酮与碳酸钾的质量比为1：(2-20)。
根据本发明，优选的，步骤(2)中4,4′-双-长链烷氧基二苯甲酮的质量与水合肼的体积比为1：(1-10)g/mL；
优选的，4,4′-双-长链烷氧基二苯甲酮与水合肼的反应过程中以乙醇为溶剂，乙酸为催化剂，于70-100℃反应10-100h；进一步优选的，4,4′-双-长链烷氧基二苯甲酮的质量与乙醇的体积之比为1：(10-100)g/mL，4,4′-双-长链烷氧基二苯甲酮的质量与乙酸的体积比为1：(0.05-0.5)g/mL。
根据本发明，优选的，步骤(2)中4,4′-双-长链烷氧基二苯甲酮腙的氧化反应过程中使用的氧化剂为二氧化锰、吸水剂为无水硫酸钠、碱为氢氧化钾。
优选的，4,4′-双-长链烷氧基二苯甲酮腙、二氧化锰、无水硫酸钠和氢氧化钾的质量比为1：(0.2-2)：(0.25-1)：(0.01-0.1)；
优选的，反应过程中避光反应，反应温度为-40-40℃，反应时间为1-10h。
根据本发明，优选的，步骤(3)中热处理温度为100-140℃，热处理时间为10-30min。
本发明的原理：
本发明另辟新径，用长链烷基重氮甲烷对已经成型的聚氨酯-纳米银材料进行表面修饰，使其表面均匀覆盖一层疏水基团，形成了纳米银与水分子的屏障，抑制水分子与纳米银接触，从而赋予聚氨酯-纳米银材料长效抗菌性质。由于现行的疏水性聚氨酯的制备难度大，因此本发明将会扩大聚氨酯抗菌材料的应用领域。
本发明的长链烷基重氮甲烷在加热后会生成高活性卡宾，然后迅速与聚氨酯-纳米银薄膜表面的羧基发生反应，且与聚氨酯链的C-H键发生插入反应，把长链烷基修饰到聚氨酯表面，使其表面具有疏水性。
本发明长链烷基重氮甲烷的合成与聚氨酯-纳米银薄膜的修饰的原理如下：
本发明的有益效果如下：
1、本发明在聚氨酯制备过程中加入硝酸银，由于聚氨酯和硝酸银都是以溶液的形式存在，硝酸银在后续热处理过程中还原成纳米银，使得纳米银分散均匀，大分子的聚氨酯链也限制了纳米银的团聚。
2、本发明通过先制备聚氨酯-纳米银抗菌薄膜，然后利用高分子链自身的C-H键和水性聚氨酯自带的羧基实现聚氨酯材料的疏水性表面修饰。即不必预先在聚氨酯分子内引入高活性反应基团，简化了反应过程，同时避免了疏水性聚氨酯合成难度大的问题。
3、本发明制得的聚氨酯-纳米银长效抗菌薄膜具有良好的长效抗菌性，经过修饰后的薄膜中的Ag+在水溶液中的释放速率变慢。通过聚氨酯-纳米银长效抗菌薄膜水分散体电导率测试，48h电导率增加仅110％，而普通聚氨酯-纳米银抗菌薄膜48h电导率增加达220％。说明本发明的聚氨酯抗菌薄膜达到了长效抗菌的效果。
4、本发明制得的聚氨酯-纳米银长效抗菌薄膜具有良好的抗菌性能，通过对大肠杆菌、金黄色葡萄球菌的抗菌性能测试，本发明的聚氨酯-纳米银长效抗菌薄膜的抑菌圈直径与普通聚氨酯抗菌薄膜抑菌圈直径相仿。
附图说明
图1为试验例3中不含纳米银的聚氨酯薄膜的扫描电镜照片。
图2为试验例3中聚氨酯-纳米银薄膜的扫描电镜照片。
图3为对比例1中聚氨酯-纳米银薄膜的扫描电镜照片。
具体实施方式
下面通过具体实施例对本发明做进一步说明，但不限于此。
实施例中所用原料如无特殊说明，均为常规市购产品。
实施例1-3
一种热处理后修饰法制备聚氨酯-纳米银长效抗菌薄膜的方法，包括步骤如下：
(1)聚氨酯-纳米银薄膜的制备
在一个100mL的三口瓶中加入4,4′-二环己基甲烷二异氰酸酯(7.5g)和聚四氢呋喃(7.9g)，用数显电动搅拌器恒温90℃下搅拌2小时进行预聚合反应，反应完毕后将温度降至70℃；将三羟甲基丙烷(0.178g)、1,6-己二醇(2.21g)溶于丙酮(15mL)中并倒入三口烧瓶中，之后加入二羟甲基丙酸(0.180g)，二月硅酸二丁基锡3滴，温度升至80℃继续反应3h。然后，将质量百分数分别为1％(实施例1)、5％(实施例2)、10％(实施例3)的硝酸银固体溶于二甲基甲酰胺(5mL)，再用滴管分批加入聚氨酯溶液中，在室温下继续搅拌30min。混合溶液均匀地倒入聚四氟乙烯模具中，在电热鼓风干燥箱中进行热处理。热处理的过程依次为：25℃(50min)→120℃(80min)→160℃(130min)→180℃(10min)。所用的各原料的比例如表1所示。
表1 不同原料比例的PU薄膜的配方
(2)长链烷基重氮甲烷的合成
①4,4′-双-十二烷氧基二苯甲酮的合成
在单口烧瓶中加入二甲基甲酰胺(30mL)，4,4′-二羟基二苯甲酮(2.14g,0.01mol)，1-溴代十二烷(5g,0.02mol)，碳酸钾(6.9g,0.05mol)，在80℃下反应24h，然后回流搅拌24h，反应完毕后冷却至室温，得到白色絮状物固体，在真空干燥箱中干燥12h。Yield:70％；1H-NMR：0.878(t,3H,-CH2CH3),1.238(m,2H,-CH2-CH2),1.465(m,2H,O-CH2-CH2-CH 2)，1.789(m,2H,O-CH2 CH 2),4.040(t,2H,O-CH 2),6.962(d,1H,ph-H),7.794(d,1H,ph-H)；13C-NMR(50MHz,CDCl3):193.8(1C,CO)161.9,131.6,130.1,113.4(4C,C-ph),67.8(1C,O-CH2),31.3,29.1,28.8,25.5(4C,-CH2),22.1(1C,-CH2CH3),13.5(1C,-CH2 CH3)；IR(KBr,cm-1):3398.57,2954.95,2850.79,1633.71,1602.85,1309.67,1253.73.
②4,4′-双-十二烷氧基二苯甲酮腙的合成
将第一步反应后的固体(1.39g,2.53mmol)溶于20mL的乙醇中，倒入100mL的单口瓶中，加入水合肼(2.45mL,50.6mmol)，再加入几滴冰乙酸(0.4mL)作为催化剂，加热至80℃回流搅拌48h，反应完毕后把乙醇蒸干，然后将其溶于二氯甲烷(60mL)中，用蒸馏水(60mL)洗涤4次，加入无水硫酸镁干燥有机层，旋蒸得到淡黄色固体，在真空干燥箱中干燥24h。Yield:75％；1H-NMR：0.88(t,3H,-CH2-CH 3),1.277(m,2H,-CH 2CH3),1.453(m,2H,O-CH 2),1.754(m,2H,O-CH2-CH 2),4.06(t,2H,O-CH2),7.0(s,2H,C＝N-NH2),7.405,7.248,7.023,6.837(d,1H,ph-H)；12C-NMR：158.9(1C,C＝N),161.9,130.9,124.4,114.6(4C,C-ph),67.7(1C,O-CH2),31.4(1C,-CH2-CH2-CH3),29.1(4C,-CH2),25.6(1C,O-CH2-CH2-CH2),13.6(1C,-CH2-CH3).IR(KBr:cm-1):3471.86,2954.95,2850.79,1604.71,1508.33,1247.94.
③4,4′-双-十二烷氧基重氮甲烷的合成
将第二步产物(1.015g,1.8mmol)溶于二氯甲烷(15mL)中，加入二氧化锰(0.57g,6.51mmol)，无水硫酸钠(0.50g,3.50mmol)，氢氧化钾(0.15g,2.75mmol)，在室温下避光搅拌2h，反应完毕后抽滤，有机层经旋蒸后将得到紫色固体。Yield:50％；1H-NMR：0.89(t,3H,-CH2-CH 3),1.26(m,2H,-CH 2),1.29(m,2H,-CH2),1.43(m,2H,O-CH2-CH2-CH 2),1.77(m,2H,O-CH2-CH 2),3.97(t,2H,O-CH 2),6.95(d,1H,ph-H),7.19(d,1H,ph-H)。13C-NMR：156.8,126.0,120.8,114.9(4C,C-ph),67.7(1C,O-CH2),31.4(1C,-CH2-CH2-CH3),29.1(4C,-CH2),25.6(1C,O-CH2-CH2-CH2),13.6(1C,-CH2CH3).IR(KBr:cm-1):3361.93,2918.30,2852.72,2059.71,1510.26,1473.62,1249.87,1024.20.
(3)聚氨酯-纳米银薄膜的表面修饰
先将步骤(1)制备好的聚氨酯-纳米银薄膜切成2×2cm的小方块。然后采用热处理法对薄膜进行表面修饰：
热处理法：首先将4,4′-双-十二烷氧基重氮甲烷(0.1g)上溶于的环己烷(15mL)中，然后用胶头滴管将溶液滴到薄膜的表面，待溶剂挥发干净后，将薄膜放入温度为120℃电热鼓风干燥箱中加热10min，冷却至室温后用环己烷冲洗薄膜。
实施例4
如实施例1所述，不同的是：
步骤(1)中预聚合反应温度为100℃，加入二羟甲基丙酸和二月硅酸二丁基锡后反应温度为70℃；
步骤(3)中热处理温度为140℃。
实施例5
如实施例1所述，不同的是：
步骤(1)中二异氰酸酯、聚四氢呋喃、交联剂、扩链剂、二羟甲基丙酸和催化剂的质量比为1：1.1：0.024：0.28：0.02：0.003。
对比例1
①在一个100mL的三口瓶中加入4,4′-二环己基甲烷二异氰酸酯(7.5g)和聚四氢呋喃(7.9g)，用数显电动搅拌器恒温90℃下搅拌2小时进行预聚合反应，反应完毕后将温度降至70℃；将三羟甲基丙烷(0.178g)、1,6-己二醇(2.21g)溶于丙酮(15mL)中并倒入三口烧瓶中，之后加入二羟甲基丙酸(0.180g)，二月硅酸二丁基锡3滴，温度升至80℃继续反应3h，得到聚氨酯溶液。
②将聚乙烯吡咯烷酮(10.5g)加入到乙二醇(49.8mL)中加热至60℃，搅拌使聚乙烯吡咯烷酮全部溶解，然后加入AgNO3(1.5g)，升温至120℃继续搅拌反应1.5h，反应完成后冷却至室温，即得银纳米颗粒溶液。
③取如②所述的纳米颗粒溶液10mL，加入到如①所述的聚氨酯溶液中，在室温下搅拌0.5h。然后，将混合溶液均匀地倒入聚四氟乙烯模具中，在50℃的电热鼓风干燥箱中进行干燥，得到聚氨酯-纳米银对比薄膜，电镜照片如图3所示。
试验例1、抗菌实验
培养基的配制：称取蛋白胨(3.5g)、NaCl(1.75g)、酵母粉(1.75g)、琼脂粉(3g)放入锥形瓶中，加入蒸馏水(350mL)溶解。用NaOH水溶液(1M)调节pH值至7.2左右，高压灭菌30min(121℃，1.41MPa)，然后在电热恒温培养箱中恒温于60℃培养12h，以便于倾倒。
抗菌实验：首先将大肠杆菌或金黄色葡萄球菌(2mL)接种到培养基溶液上，然后将培养基倒入无菌培养皿。待培养基冷却凝固后，将直径为1.2mm的聚氨酯-纳米银薄膜圆片放入培养基上，在培养箱中培养24h后测量抑菌圈的直径。
本试验例中将不同银含量的聚氨酯-纳米银薄膜经热处理法修饰后，测试对大肠杆菌、金黄色葡萄球菌的抗菌性能，并与修饰前的薄膜进行对比，结果如表2所示。
从表2中可以看出：
a.聚氨酯薄膜的抑菌圈直径没有发生变化，说明该薄膜无抗菌性。
b.聚氨酯-纳米银薄膜的抑菌圈的直径增大，说明该薄膜具有抗菌性。
c.随着硝酸银含量的增加，聚氨酯-纳米银薄膜的抑菌圈的直径也增大，说明硝酸银含量越大，聚氨酯-纳米银薄膜的抗菌性能越好。
d.聚氨酯-纳米银薄膜在热处理修饰前后的抑菌圈直径大小相仿。
表2 聚氨酯-纳米银薄膜的抗菌实验数据
试验例2、电导率实验
将表面为长链烷基修饰的聚氨酯-纳米银薄膜置于蒸馏水(30mL)中，在25℃下恒温搅拌，隔时测定水溶液的电导率。
为了观察聚氨酯-纳米银薄膜经表面修饰后，银离子在水中的释放速率是否减慢，即是否具有长效抗菌性质，研究了银含量为10％的聚氨酯-纳米银薄膜在水溶液中的电导率的变化。电导率的测试数据如表3所示。
表3 银含量为10％的聚氨酯-纳米银薄膜的电导率数据
表3的数据表明，当银含量为10％时，薄膜的电导率大小比较为：未修饰的聚氨酯薄膜<热处理法修饰的聚氨酯-纳米银薄膜。因此，经过修饰后的薄膜中的Ag+在水溶液中的释放速率变慢，即达到了长效抗菌的效果。
试验例3、聚氨酯-纳米银薄膜的表面形貌
图1为不含纳米银的聚氨酯薄膜的扫描电镜照片，图2为试验例3的聚氨酯-纳米银薄膜的扫描电镜照片，图3为对比例1的聚氨酯-纳米银薄膜的扫描电镜照片。由于银的还原电位低(E0＝0.8V)，因而硝酸银在加热时就可以还原为Ag单质。通过对比图1、2发现，当无纳米银时，薄膜表面无任何物质；当银含量为10％时，薄膜内部有大量的纳米银颗粒，这说明加入的硝酸银经热处理后还原成了纳米银。
通过对比图2、3发现，当硝酸银在聚氨酯链的间隙中被原位还原成纳米银时，聚氨酯的大分子链限制了纳米银的团聚，使纳米银颗粒分散得较为均匀；而把纳米银与聚氨酯共混时(对比例1)，纳米银在聚氨酯体系中分散不太均匀，有较为严重的团聚现象。
Claims (10)
1.一种热处理后修饰法制备聚氨酯-纳米银长效抗菌薄膜的方法，包括步骤如下：
(1)聚氨酯-纳米银薄膜的制备
将二异氰酸酯和聚四氢呋喃混合，于80-120℃反应1-10h；加入交联剂、扩链剂，再加入二羟甲基丙酸和催化剂，于60-90℃反应1-10h，得聚氨酯溶液(PU)；
向聚氨酯溶液中加入硝酸银的二甲基甲酰胺溶液，搅拌均匀后成膜，再进行热处理，即得聚氨酯-纳米银薄膜；
(2)长链烷基重氮甲烷的制备
将4,4′-二羟基二苯甲酮与长链卤代烷反应，得4,4′-双-长链烷氧基二苯甲酮；4,4′-双-长链烷氧基二苯甲酮与水合肼反应得4,4′-双-长链烷氧基二苯甲酮腙；4,4′-双-长链烷氧基二苯甲酮腙经氧化反应得长链烷基重氮甲烷；
(3)聚氨酯-纳米银长效抗菌薄膜的制备
将长链烷基重氮甲烷溶于溶剂中，均匀涂覆到聚氨酯-纳米银薄膜表面，于100-250℃热处理1-60min，即得聚氨酯-纳米银长效抗菌薄膜。
2.根据权利要求1所述的热处理后修饰法制备聚氨酯-纳米银长效抗菌薄膜的方法，其特征在于，步骤(1)中所述的二异氰酸酯为4,4′-二环己基甲烷二异氰酸酯，所述的交联剂为三羟甲基丙烷，所述的扩链剂为1,6-己二醇，所述的催化剂为二月硅酸二丁基锡。
3.根据权利要求1所述的热处理后修饰法制备聚氨酯-纳米银长效抗菌薄膜的方法，其特征在于，步骤(1)中二异氰酸酯、聚四氢呋喃、交联剂、扩链剂、二羟甲基丙酸和催化剂的质量比为1：(0.8-1.2)：(0.01-0.1)：(0.1-1)：(0.01-0.1)：(0.001-0.01)。
4.根据权利要求1所述的热处理后修饰法制备聚氨酯-纳米银长效抗菌薄膜的方法，其特征在于，步骤(1)中硝酸银的加入量为聚氨酯溶液质量的1-20％，硝酸银的二甲基甲酰胺溶液中硝酸银的质量与二甲基甲酰胺的体积之比为1：(1-10)g/mL。
5.根据权利要求1所述的热处理后修饰法制备聚氨酯-纳米银长效抗菌薄膜的方法，其特征在于，步骤(2)中所述的长链卤代烷为1-溴代十二烷；
优选的，4,4′-二羟基二苯甲酮与长链卤代烷的质量比为1：(2-20)。
6.根据权利要求1所述的热处理后修饰法制备聚氨酯-纳米银长效抗菌薄膜的方法，其特征在于，步骤(2)中反应温度为80-200℃，反应时间为10-100h。
7.根据权利要求1所述的热处理后修饰法制备聚氨酯-纳米银长效抗菌薄膜的方法，其特征在于，步骤(2)中4,4′-双-长链烷氧基二苯甲酮的质量与水合肼的体积比为1：(1-10)g/mL；
优选的，4,4′-双-长链烷氧基二苯甲酮与水合肼的反应过程中以乙醇为溶剂，乙酸为催化剂，于70-100℃反应10-100h；
进一步优选的，4,4′-双-长链烷氧基二苯甲酮的质量与乙醇的体积之比为1：(10-100)g/mL，4,4′-双-长链烷氧基二苯甲酮的质量与乙酸的体积比为1：(0.05-0.5)g/mL。
8.根据权利要求1所述的热处理后修饰法制备聚氨酯-纳米银长效抗菌薄膜的方法，其特征在于，步骤(2)中4,4′-双-长链烷氧基二苯甲酮腙的氧化反应过程中使用的氧化剂为二氧化锰、吸水剂为无水硫酸钠、碱为氢氧化钾。
9.根据权利要求8所述的热处理后修饰法制备聚氨酯-纳米银长效抗菌薄膜的方法，其特征在于，步骤(2)中4,4′-双-长链烷氧基二苯甲酮腙、二氧化锰、无水硫酸钠和氢氧化钾的质量比为1：(0.2-2)：(0.25-1)：(0.01-0.1)；
优选的，反应过程中避光反应，反应温度为-40-40℃，反应时间为1-10h。
10.根据权利要求1所述的热处理后修饰法制备聚氨酯-纳米银长效抗菌薄膜的方法，其特征在于，步骤(3)中热处理温度为100-140℃，热处理时间为10-30min。
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108755112A (zh) * | 2018-06-27 | 2018-11-06 | 济南鸿湾生物技术有限公司 | 一种高分子材料的抗菌改性方法 |
| CN109106989A (zh) * | 2018-09-14 | 2019-01-01 | 太和县中科蓝海智能医疗设备有限公司 | 一种医用导管超疏水聚氨酯-纳米银-聚乙二醇抗菌薄膜的制备方法 |
| CN109280366A (zh) * | 2018-08-14 | 2019-01-29 | 江苏宏远新材料科技有限公司 | 一种抗菌性防水透湿聚氨酯薄膜的制备方法 |
| CN110186898A (zh) * | 2019-06-06 | 2019-08-30 | 齐鲁工业大学 | 一种疏水性纸质表面增强拉曼基底及其应用 |
| CN110862503A (zh) * | 2019-11-29 | 2020-03-06 | 佛山市瑞福物联科技有限公司 | 一种导电聚氨酯预聚体的制备方法及其导电胶 |
| CN113582829A (zh) * | 2021-08-04 | 2021-11-02 | 武汉大学 | 一种基于二苯甲酮类的柔性室温磷光晶体及其制备方法和其应用 |
| CN114524916A (zh) * | 2020-04-24 | 2022-05-24 | 厦门长塑实业有限公司 | 一种架桥剂及其制备方法、水性聚氨酯混合液及其制备方法 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010057080A1 (en) * | 2008-11-17 | 2010-05-20 | Dsm Ip Assets B.V. | Surface modification of polymers via surface active and reactive end groups |
| CN106432778A (zh) * | 2011-07-18 | 2017-02-22 | 赛尔格有限责任公司 | 表面改性聚合材料、改性官能化聚合物、功能聚合物和方法 |
-
2017
- 2017-05-15 CN CN201710339632.4A patent/CN107163280B/zh active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010057080A1 (en) * | 2008-11-17 | 2010-05-20 | Dsm Ip Assets B.V. | Surface modification of polymers via surface active and reactive end groups |
| CN106432778A (zh) * | 2011-07-18 | 2017-02-22 | 赛尔格有限责任公司 | 表面改性聚合材料、改性官能化聚合物、功能聚合物和方法 |
Non-Patent Citations (2)
| Title |
|---|
| JINKU XU ET AL.: "Radical/Addition Polymerization Silicone Hydrogels with Simultaneous Interpenetrating Hydrophilic/Hydrophobic Networks", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| 于溪等: "于溪等", 《高分子材料科学与工程》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108755112A (zh) * | 2018-06-27 | 2018-11-06 | 济南鸿湾生物技术有限公司 | 一种高分子材料的抗菌改性方法 |
| CN108755112B (zh) * | 2018-06-27 | 2020-09-25 | 济南鸿湾生物技术有限公司 | 一种高分子材料的抗菌改性方法 |
| CN109280366A (zh) * | 2018-08-14 | 2019-01-29 | 江苏宏远新材料科技有限公司 | 一种抗菌性防水透湿聚氨酯薄膜的制备方法 |
| CN109106989A (zh) * | 2018-09-14 | 2019-01-01 | 太和县中科蓝海智能医疗设备有限公司 | 一种医用导管超疏水聚氨酯-纳米银-聚乙二醇抗菌薄膜的制备方法 |
| CN110186898A (zh) * | 2019-06-06 | 2019-08-30 | 齐鲁工业大学 | 一种疏水性纸质表面增强拉曼基底及其应用 |
| CN110862503A (zh) * | 2019-11-29 | 2020-03-06 | 佛山市瑞福物联科技有限公司 | 一种导电聚氨酯预聚体的制备方法及其导电胶 |
| CN110862503B (zh) * | 2019-11-29 | 2022-02-11 | 佛山市瑞福物联科技有限公司 | 一种导电聚氨酯预聚体的制备方法及其导电胶 |
| CN114524916A (zh) * | 2020-04-24 | 2022-05-24 | 厦门长塑实业有限公司 | 一种架桥剂及其制备方法、水性聚氨酯混合液及其制备方法 |
| CN114524916B (zh) * | 2020-04-24 | 2023-12-01 | 福建长塑实业有限公司 | 一种架桥剂及其制备方法、水性聚氨酯混合液及其制备方法 |
| CN113582829A (zh) * | 2021-08-04 | 2021-11-02 | 武汉大学 | 一种基于二苯甲酮类的柔性室温磷光晶体及其制备方法和其应用 |
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