CN116285643A - 一种高强度超韧有机硅改性聚氨酯防污涂层及其制备方法 - Google Patents
一种高强度超韧有机硅改性聚氨酯防污涂层及其制备方法 Download PDFInfo
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Abstract
本发明涉及海洋防污涂料技术,旨在提供一种高强度超韧有机硅改性聚氨酯防污涂层及其制备方法,用于解决现有有机硅低表面能防污涂层力学性能差,静态防污能力弱等技术问题。本发明以聚硅氧烷和聚四氢呋喃作为聚氨酯的软段,二异氰酸酯作为硬段,在催化剂、扩链剂和交联固化剂的作用下室温固化成型。其具体制备方法为:在有机锡催化剂作用下,将聚硅氧烷、聚四氢呋喃、二异氰酸酯混合均匀,反应生成异氰酸酯基终端的预聚体,再将预聚体依次与扩链剂、交联固化剂反应,即得有机硅改性聚氨酯防污涂层。该防污涂层制备过程简易,对生态环境友好,绿色环保,在海洋防污领域具有广泛的应用前景。
Description
技术领域
本发明属于海洋防污领域,涉及一种高强度超韧有机硅改性聚氨酯防污涂层及其制备方法。
背景技术
海洋生物污损是指海洋微生物、动物、植物在海水以下表面附着、生长、繁殖而形成的生物垢,它给海洋设施和海洋开发带来诸多的问题。生物垢会增加船舶航行阻力,降低其航行速度,增加燃油消耗以及温室气体排放,而且附着的生物会随着船只迁移到其他海域,带来生物入侵的问题;它也会加速金属结构腐蚀,给海上采油平台等海洋开采装备带来安全隐患;生物污损还会阻塞核电站、抽海水蓄能电站等能源设施的海水冷却管道,降低冷却效率;同时,也会阻塞海产养殖网箱的网孔,阻碍营养物质的输送,降低产量。可见,防治海洋生物污损对于海洋开发具有重要的保障作用。
在众多海洋防污方法中,涂装防污涂料是最有效、经济、便捷的方法。按照是否释放防污剂,防污涂料可以分为杀生型和非杀生型。前者含有毒性防污剂,依靠防污剂的不断释放,达到杀死或驱散污损生物的目的。随着人们环保意识的提高,防污剂的使用在多个国家受到法规严格审查,非杀生型防污涂料受到人们越来越多的关注,其中最具有应用前景的是污损脱附型涂料(FRCs)。FRCs大多是基于有机硅弹性体,特别是聚二甲基硅氧烷(PDMS)。它具有低表面能、高弹性、低表面粗糙度的特点,因此污损生物不易附着在涂层表面,或者附着不牢固,在强水流的冲刷作用下易于从涂层表面脱除,不依靠防污剂即达到防污效果,生态友好。然而,有机硅材料静态防污能力差,质软,力学性能差,很容易在服役过程中破损,从而导致涂层失效。其中,Peng等报道了一种生物启发的自分层涂层,该涂层由具有多巴胺和硅烷基的聚氨酯和具有氟碳化合物和聚乙二醇链段的双硅烷醇封端的聚(二甲基硅氧烷)组成,其中具有氟碳化合物和聚乙二醇链段的双硅烷醇封端的聚(二甲基硅氧烷)作为反应性两亲聚合物(RAP)。在涂层形成过程中,由于自分层效应,低表面能的RAP可以在表面富集,而多巴胺和硅烷基团赋予涂层较强的基材附着力。但其拉伸强度仅为30-40KPa,还有较大的提升空间,且其实验制备过程复杂,难以实现工业化生产,有待改进(Peng Hu,Ru Xie,Qingyi Xie,Chunfeng Ma,Guangzhao Zhang.Simultaneousrealization of antifouling,self-healing,and strong substrate adhesion via abioinspired self-stratification strategy[J].Chemical Engineering Journal,2022,137875.)。Sheng等研制了一种具有Zn(II)-羧基和Zn(II)-二胺吡啶双金属配位结构的耐刮自愈水性聚氨酯-尿素涂层。锌离子的加入使涂层表面形成了致密的金属配位键,大大提高了涂层表面硬度(从B提高到4H)和抗刮擦性,而内层由于金属离子渗透较少,与基材保持了良好的附着力(>1.5MPa)。但其含有金属离子,存在金属离子析出的潜在问题,对海洋生态环境造成危害(Yeming Sheng,Minhui Wang,Kangping Zhang,Zhenyu Wu,YaxinChen,Xun Lu.An“inner soft external hard”,scratch-resistant,self-healingwaterborne poly(urethane-urea)coating based on gradient metal coordinationstructure[J].Chemical Engineering Journal,2021,131883.)。
发明内容
针对现有技术的不足,为了提高有机硅低表面能防污涂层的力学性能以及静态防污能力,本发明提供了一种高强度超韧有机硅改性聚氨酯防污涂层及其制备方法。
根据本发明,一种高强度超韧有机硅改性聚氨酯防污涂层,由聚硅氧烷、聚四氢呋喃、二异氰酸酯、扩链剂和交联固化剂反应制得。具体步骤如下:
(1)取一三颈烧瓶,将聚硅氧烷,聚四氢呋喃,二异氰酸酯和催化剂溶于有机溶剂中,在一定温度下反应一段时间,生成异氰酸酯基终端的预聚体;
(2)将一定量的扩链剂加入至步骤(1)中的反应体系中,在一定温度下反应一段时间,得到中间产物;
(3)将一定量的交联固化剂加入至步骤(2)中的反应体系中,在一定温度下反应一段时间,得到反应产物;
(4)将步骤(3)中的最终反应产物滴涂在不同基底上制备防污涂层。
根据本发明,步骤(1)中聚硅氧烷为羟基双封端聚二甲基硅氧烷(分子量为2000-3500);二异氰酸酯为异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、二环己基甲烷二异氰酸酯(HMDI)、二苯基甲烷二异氰酸酯(MDI)和六亚甲基二异氰酸酯(HDI)中的一种或几种;所述催化剂为二月桂酸二丁基锡(DBTDL)和二乙酸二丁基锡中的一种或多种;所述有机溶剂为丙酮;所述反应温度为80℃;反应时间为2h;聚硅氧烷和聚四氢呋喃用量之比为n=1:1;体系中R值(nNCO/nOH)为1.3~1.5。
根据本发明,步骤(2)中扩链剂为2,2-二羟甲基丙酸(DMPA)和2,2-二羟甲基丁酸(DMBA)中的一种或几种;所述反应温度为80℃;反应时间为2h。
根据本发明,步骤(3)中交联固化剂为γ-氨丙基三乙氧基硅烷(KH-550)、γ-氨丙基三甲氧基硅烷(KH-450)和N-苯基-γ-氨丙基三甲氧基硅烷中的一种或几种;所述反应温度为80℃;反应时间为2h。
根据本发明,步骤(2)中扩链剂物质的量和步骤(3)中交联固化剂物质的量的比值范围为0.2:1.8~1:1,即n(扩链剂):n(交联固化剂)=0.2:1.8~1:1。
与现有技术相比,本发明的有益效果在于:
(1)本发明中基于有机硅改性聚氨酯防污涂层,反应条件简易,反应步骤简便,具有可控性,较容易设计分子结构;
(2)本发明通过引入扩链剂提高了涂层的力学强度和韧性,其中最佳样品(DMBA:KH-550=0.7:1.3)拉伸强度可达2.962MPa,断裂伸长率可达550%。
附图说明
图1为本发明实施例2制得的有机硅改性聚氨酯防污涂层的水接触角测试结果。
图2为本发明实施例2制得的有机硅改性聚氨酯防污涂层的表面自由能测试结果。
图3为本发明实施例2制得的有机硅改性聚氨酯防污涂层的力学性能测试结果。
图4为本发明实施例2制得的有机硅改性聚氨酯防污涂层与基材附着力测试结果。
图5为本发明实施例2制得的有机硅改性聚氨酯防污涂层的自清洁测试结果。
具体实施方式
下面结合具体实施例和附图对本发明做进一步的说明,但不限于此。
同时下述实施例中所述实验方法,如无特殊说明,均为常规方法;所述试剂和材料,如无特殊说明,均可从商业途径获得。
实施例1:
取一三颈烧瓶,将羟基双封端聚二甲基硅氧烷(3.7500mmol),PTMG(3.7500mmol),IPDI(9.7500mmol)和DBTDL溶于丙酮中,在80℃下反应2h,生成异氰酸酯基终端的预聚体溶液;将DMBA(1.500mmol)加入至上述预聚体溶液中,在80℃下反应2h,得到中间产物溶液;然后将KH-550(1.500mmol)加入至上述中间产物溶液中,在80℃下反应2h,得到反应产物溶液;将反应产物滴涂在不同基底上制备防污涂层。制得的防污涂层在室温下固化成型,并将其命名为DMBA:KH-550=1:1。
本实施例制得的防污涂层的水接触角测试结果如图1所示。
本实施例制得的防污涂层的表面自由能测试结果如图2所示,根据表面能与污垢释放曲线的关系,即Baier曲线,较好污损脱附性能对应的表面能区间大致在22-30mN/m,而本实施例制得的涂层表面自由能为29.99mN/m,符合最佳区间。
本实施例制得的防污涂层的力学性能测试结果如图3所示。
本实施例制得的防污涂层与基材附着力测试结果如图4所示。
实施例2:
取一三颈烧瓶,将羟基双封端聚二甲基硅氧烷(3.7500mmol),PTMG(3.7500mmol),IPDI(9.7500mmol)和DBTDL溶于丙酮中,在80℃下反应2h,生成异氰酸酯基终端的预聚体溶液;将DMBA(1.1667mmol)加入至上述预聚体溶液中,在80℃下反应2h,得到中间产物溶液;然后将KH-550(2.1667mmol)加入至上述中间产物溶液中,在80℃下反应2h,得到反应产物溶液;将反应产物滴涂在不同基底上制备防污涂层。制得的防污涂层在室温下固化成型,并将其命名为DMBA:KH-550=0.7:1.3。
本实施例制得的防污涂层的水接触角测试结果如图1所示。
本实施例制得的防污涂层的表面自由能测试结果如图2所示,根据表面能与污垢释放曲线的关系,即Baier曲线,较好污损脱附性能对应的表面能区间大致在22-30mN/m,而本实施例制得的涂层表面自由能为25.57mN/m,符合最佳区间。
本实施例制得的防污涂层的力学性能测试结果如图3所示。
本实施例制得的防污涂层与基材附着力测试结果如图4所示。
本实施例制得的防污涂层的自清洁测试结果如图5所示。图5a、图5c为去离子水滴加之前的图片,图5b、图5d为去离子水滴加之后的图片。(自清洁测试方法:将反应结束后的聚合物溶液涂在玻璃上,涂层厚度为800微米,待涂层固化成型后,将涂层的倾斜度设置约为15°,用滴管将污损液滴滴在涂层表面,在污损液滴的上方滴加去离子水以去除污损物。)性能评价结果:从图5b和图5d可以看出,污损液滴被去离子水溶解并从涂层表面滑落,这说明在应用中各种无机污染物可以在水流作用下从涂层表面去除,涂层具有一定的自清洁性能。
实施例3:
取一三颈烧瓶,将羟基双封端聚二甲基硅氧烷(3.7500mmol),PTMG(3.7500mmol),IPDI(9.7500mmol)和DBTDL溶于丙酮中,在80℃下反应2h,生成异氰酸酯基终端的预聚体溶液;将DMBA(0.9000mmol)加入至上述预聚体溶液中,在80℃下反应2h,得到中间产物溶液;然后将KH-550(2.7000mmol)加入至上述中间产物溶液中,在80℃下反应2h,得到反应产物溶液;将反应产物滴涂在不同基底上制备防污涂层。制得的防污涂层在室温下固化成型,并将其命名为DMBA:KH-550=0.5:1.5。
本实施例制得的防污涂层的水接触角测试结果如图1所示。
本实施例制得的防污涂层的表面自由能测试结果如图2所示,根据表面能与污垢释放曲线的关系,即Baier曲线,较好污损脱附性能对应的表面能区间大致在22-30mN/m,而本实施例制得的涂层表面自由能为25.58mN/m,符合最佳区间。
本实施例制得的防污涂层的力学性能测试结果如图3所示。
本实施例制得的防污涂层与基材附着力测试结果如图4所示。
实施例4:
取一三颈烧瓶,将羟基双封端聚二甲基硅氧烷(3.7500mmol),PTMG(3.7500mmol),IPDI(9.7500mmol)和DBTDL溶于丙酮中,在80℃下反应2h,生成异氰酸酯基终端的预聚体溶液;将DMBA(0.5870mmol)加入至上述预聚体溶液中,在80℃下反应2h,得到中间产物溶液;然后将KH-550(3.3260mmol)加入至上述中间产物溶液中,在80℃下反应2h,得到反应产物溶液;将反应产物滴涂在不同基底上制备防污涂层。制得的防污涂层在室温下固化成型,并将其命名为DMBA:KH-550=0.3:1.7。
本实施例制得的防污涂层的水接触角测试结果如图1所示。
本实施例制得的防污涂层的表面自由能测试结果如图2所示,根据表面能与污垢释放曲线的关系,即Baier曲线,较好污损脱附性能对应的表面能区间大致在22-30mN/m,而本实施例制得的涂层表面自由能为25.61mN/m,符合最佳区间。
本实施例制得的防污涂层的力学性能测试结果如图3所示。
本实施例制得的防污涂层与基材附着力测试结果如图4所示。
Claims (5)
1.根据本发明,一种高强度超韧有机硅改性聚氨酯防污涂层,由聚硅氧烷、聚四氢呋喃、二异氰酸酯、扩链剂和交联固化剂反应制得。具体步骤如下:
(1)取一三颈烧瓶,将聚硅氧烷,聚四氢呋喃,二异氰酸酯和催化剂溶于有机溶剂中,
在一定温度下反应一段时间,生成异氰酸酯基终端的预聚体;
(2)将一定量的扩链剂加入至步骤(1)中的反应体系中,在一定温度下反应一段时间,得到中间产物;
(3)将一定量的交联固化剂加入至步骤(2)中的反应体系中,在一定温度下反应一段时间,得到反应产物;
(4)将步骤(3)中的最终反应产物滴涂在不同基底上制备防污涂层。
2.根据本发明,步骤(1)中聚硅氧烷为羟基双封端聚二甲基硅氧烷(分子量为2000-3500);二异氰酸酯为异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、二环己基甲烷二异氰酸酯(HMDI)、二苯基甲烷二异氰酸酯(MDI)和六亚甲基二异氰酸酯(HDI)中的一种或几种;所述催化剂为二月桂酸二丁基锡(DBTDL)和二乙酸二丁基锡中的一种或多种;所述有机溶剂为丙酮;所述反应温度为80℃;反应时间为2h;聚硅氧烷和聚四氢呋喃用量之比为n=1:1;体系中R值(nNCO/nOH)为1.3~1.5。
3.根据本发明,步骤(2)中扩链剂为2,2-二羟甲基丙酸(DMPA)和2,2-二羟甲基丁酸(DMBA)中的一种或两种;所述反应温度为80℃;反应时间为2h。
4.根据本发明,步骤(3)中交联固化剂为γ-氨丙基三乙氧基硅烷(KH-550)、γ-氨丙基三甲氧基硅烷(KH-450)和N-苯基-γ-氨丙基三甲氧基硅烷中的一种或几种;所述反应温度为80℃;反应时间为2h。
5.根据本发明,步骤(2)中扩链剂物质的量和步骤(3)中交联固化剂物质的量的比值范围为0.2:1.8~1:1,即n(扩链剂):n(交联固化剂)=0.2:1.8~1:1。
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