基于聚丙烯酰胺的防污材料的制备与性能研究
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摘要
海洋生物的附着给船舶和海洋设施带来极大的危害,所以必须采取措施对其进行防除,目前最有效的途径就是涂装防污涂料。传统的防污涂料主要是以有机锡和氧化亚铜等为防污剂,由于其会在海洋中产生积累而影响海生物的生长以及海洋食物链,不仅严重危害了海洋生态环境,而且影响到了人类的健康,因此,开发新型无毒环保防污材料已迫在眉睫。
仿生防污作为一个全新的防污方法,因具有无毒无污染的特点而受到了人们的重视。众所周之,鲨鱼终日生活在海水中,但是其皮肤表面却不附着任何的污损海生物。研究发现:其表皮具有特殊的不稳定结构,能够分泌粘液在其皮肤表面形成一层粘液层,该粘液层在水流的作用下处于机械不稳定状态,所以不适合海生物的附着。本论文主要是对鲨鱼皮粘液分泌功能进行模仿,以实现对海生物附着污损的防除。具体是将含聚丙烯酰胺的材料加入到有机硅树脂中制成涂层,利用缓释控制技术使其在材料的表面少量、持续地溶出,由于聚丙烯酰胺具有水凝胶特性,因此溶出的聚丙烯酰胺会在材料的表面形成薄层水凝胶,它在海水运动的作用下会产生动态的不稳定效果,从而不利于海生物的附着,可以有效地防除污损海生物。
本论文通过对筛选的聚丙烯酰胺进行物理处理的方法和化学合成聚丙烯酰胺共聚物的方法分别与有机硅树脂相混合。对于物理方法首先是选择可以形成近似粘液状态的合适分子量范围的聚丙烯酰胺,然后对聚丙烯酰胺采取研磨的方法和添加相容剂的方法来实现聚丙烯酰胺与有机硅树脂的混合。实验表明,筛选得到的分子量为1200万的阴离子型聚丙烯酰胺AP-120与有机硅树脂不相容,添加有机硅聚醚共聚物后用锥形磨研磨能够混合均匀,但是进行硅藻培养实验时,涂片变白有脱落现象,故所采用的物理共混方法不能满足实验要求。
本论文对利用化学方法制备的聚丙烯酰胺-有机硅共聚物(COP)和聚丙烯酰胺-有机硅微球共聚物(PAS)进行了研究,结合红外光谱、热失重、释放率、迁移速率、接触角以及环境扫描电镜等手段对其进行分析与表征,并作为防污剂与有机硅树脂相混合制备了防污涂层,通过硅藻培养实验和贻贝培养实验对其防污性能进行了研究。结果显示COP凝胶比PAS凝胶在海水中保持凝胶状态的时间长,把COP与PAS分别作为防污剂加入到有机硅树脂中制成的涂层,与单纯的硅树脂相比,表面能变化较小,防污性能有显著的提高。
本论文主要是通过将聚丙烯酰胺材料加入到有机硅树脂中来实现鲨鱼皮粘液分泌功能的模仿,要最终模拟出这种材料,并使其应用于海洋防污领域,还有很多内容需要进一步深入和完善。
Biological fouling can bring about some unwanted and detrimental consequences to the marine ship and facilities. Antifouling coatings are the most reliable way to prevent the settlements of biofoulings. In the traditional antifouling paints, the primary agents such as organotin and cuprous oxide not only cause the environmental risks, but also have a harmful effect on the human health. Therefore, modern approaches to environmentally effective antifouling systerms and their performance are highlighted.
As a new method, bionical anti-fouling paints have no-toxic and non-polluting, they are more regared by more and more people. It is well known that, shark live in the sea and its skin have no marine biological fouling.The research shows that, the shark skin have a special unstable structure, and its skin can secrete mucus to form a mucus layer.In the effect of the current, the mucus layer is unstable and the marine biological hardly adhere on the shark’s skin. In this paper, the study focus on the initial stage to similate the behavior of shark skin’s secrete mucus in order to prevent the settlements of the marine biofoulings. In the dedail is that adding the polyacrylamide-based materials into the silicone resin, and marking the coating. In the sea, the polyacrylamide will migrate to the coating’s surface for the polyacrylamide’s hydrophilic nature. In the effect of the seawater, the low gel layer will become unstable, so this coating can prevent the settlements of marine fouling effectively.
In this paper, the selected polyacrylamide which is disposed by physical method and the polyacrylamide copolymer that synthesized by chemical methods mix with the silicone resin respectively.For the physical method, choosing the proper molecular weight scope polyacrylamide that can form mucus at first, and then mix the polyacrylamide and silicone resin each other by grinding method and adding phase solvent.The result shows that, the selected AP-120 and silicone resin are immiscible, and adding the silicone-polyether copolymer can realize AP-120 and silicone resin dissolved each other.The coating become while and break off when study the diatoms settlement on the coatings.So the physical method can not meet the need of the experiment.
The paper also study the Poly(acrylamide-silicone) and Poly(acrylamide-silicone) microspheres that synthesized by chemical methods. Fourier transform infrared spectrum, Thermogravimetric Analysis, melt rate, static contact angle and ESEM as the study methods to charactere and analyse the copolymers. The copolymers as the anti-fouling agent mixed with silicone resin to prepare the coatings.The coatings’s antifouling character is investigated by diatom and mussel cultivation. The result shows that, the COP gelatin can keep a longer time than the PAS gelatin in the sea, with the surface energy of silicone remaining unchanged, the restrain function for diatom and mussel adhesion is significantly improved by the addition of COP and PAS. The results of Environmental Scanning Electron Microscopic (ESEM) show that the COP and PAS on the silicone surface have changed into micro-gel after the paint immersed in the sea water, and the micro-gel structure can restrain diatom adhesion obviously.
In this paper, mainly through putting the polyacrylamide-based materials into the silicone resin to achieve the imitation of the shark skin’s mucus secretion, it is necessary to be further in-depth and improved to apply this antifouling agent into the marine antifouling field.
仿生防污作为一个全新的防污方法,因具有无毒无污染的特点而受到了人们的重视。众所周之,鲨鱼终日生活在海水中,但是其皮肤表面却不附着任何的污损海生物。研究发现:其表皮具有特殊的不稳定结构,能够分泌粘液在其皮肤表面形成一层粘液层,该粘液层在水流的作用下处于机械不稳定状态,所以不适合海生物的附着。本论文主要是对鲨鱼皮粘液分泌功能进行模仿,以实现对海生物附着污损的防除。具体是将含聚丙烯酰胺的材料加入到有机硅树脂中制成涂层,利用缓释控制技术使其在材料的表面少量、持续地溶出,由于聚丙烯酰胺具有水凝胶特性,因此溶出的聚丙烯酰胺会在材料的表面形成薄层水凝胶,它在海水运动的作用下会产生动态的不稳定效果,从而不利于海生物的附着,可以有效地防除污损海生物。
本论文通过对筛选的聚丙烯酰胺进行物理处理的方法和化学合成聚丙烯酰胺共聚物的方法分别与有机硅树脂相混合。对于物理方法首先是选择可以形成近似粘液状态的合适分子量范围的聚丙烯酰胺,然后对聚丙烯酰胺采取研磨的方法和添加相容剂的方法来实现聚丙烯酰胺与有机硅树脂的混合。实验表明,筛选得到的分子量为1200万的阴离子型聚丙烯酰胺AP-120与有机硅树脂不相容,添加有机硅聚醚共聚物后用锥形磨研磨能够混合均匀,但是进行硅藻培养实验时,涂片变白有脱落现象,故所采用的物理共混方法不能满足实验要求。
本论文对利用化学方法制备的聚丙烯酰胺-有机硅共聚物(COP)和聚丙烯酰胺-有机硅微球共聚物(PAS)进行了研究,结合红外光谱、热失重、释放率、迁移速率、接触角以及环境扫描电镜等手段对其进行分析与表征,并作为防污剂与有机硅树脂相混合制备了防污涂层,通过硅藻培养实验和贻贝培养实验对其防污性能进行了研究。结果显示COP凝胶比PAS凝胶在海水中保持凝胶状态的时间长,把COP与PAS分别作为防污剂加入到有机硅树脂中制成的涂层,与单纯的硅树脂相比,表面能变化较小,防污性能有显著的提高。
本论文主要是通过将聚丙烯酰胺材料加入到有机硅树脂中来实现鲨鱼皮粘液分泌功能的模仿,要最终模拟出这种材料,并使其应用于海洋防污领域,还有很多内容需要进一步深入和完善。
Biological fouling can bring about some unwanted and detrimental consequences to the marine ship and facilities. Antifouling coatings are the most reliable way to prevent the settlements of biofoulings. In the traditional antifouling paints, the primary agents such as organotin and cuprous oxide not only cause the environmental risks, but also have a harmful effect on the human health. Therefore, modern approaches to environmentally effective antifouling systerms and their performance are highlighted.
As a new method, bionical anti-fouling paints have no-toxic and non-polluting, they are more regared by more and more people. It is well known that, shark live in the sea and its skin have no marine biological fouling.The research shows that, the shark skin have a special unstable structure, and its skin can secrete mucus to form a mucus layer.In the effect of the current, the mucus layer is unstable and the marine biological hardly adhere on the shark’s skin. In this paper, the study focus on the initial stage to similate the behavior of shark skin’s secrete mucus in order to prevent the settlements of the marine biofoulings. In the dedail is that adding the polyacrylamide-based materials into the silicone resin, and marking the coating. In the sea, the polyacrylamide will migrate to the coating’s surface for the polyacrylamide’s hydrophilic nature. In the effect of the seawater, the low gel layer will become unstable, so this coating can prevent the settlements of marine fouling effectively.
In this paper, the selected polyacrylamide which is disposed by physical method and the polyacrylamide copolymer that synthesized by chemical methods mix with the silicone resin respectively.For the physical method, choosing the proper molecular weight scope polyacrylamide that can form mucus at first, and then mix the polyacrylamide and silicone resin each other by grinding method and adding phase solvent.The result shows that, the selected AP-120 and silicone resin are immiscible, and adding the silicone-polyether copolymer can realize AP-120 and silicone resin dissolved each other.The coating become while and break off when study the diatoms settlement on the coatings.So the physical method can not meet the need of the experiment.
The paper also study the Poly(acrylamide-silicone) and Poly(acrylamide-silicone) microspheres that synthesized by chemical methods. Fourier transform infrared spectrum, Thermogravimetric Analysis, melt rate, static contact angle and ESEM as the study methods to charactere and analyse the copolymers. The copolymers as the anti-fouling agent mixed with silicone resin to prepare the coatings.The coatings’s antifouling character is investigated by diatom and mussel cultivation. The result shows that, the COP gelatin can keep a longer time than the PAS gelatin in the sea, with the surface energy of silicone remaining unchanged, the restrain function for diatom and mussel adhesion is significantly improved by the addition of COP and PAS. The results of Environmental Scanning Electron Microscopic (ESEM) show that the COP and PAS on the silicone surface have changed into micro-gel after the paint immersed in the sea water, and the micro-gel structure can restrain diatom adhesion obviously.
In this paper, mainly through putting the polyacrylamide-based materials into the silicone resin to achieve the imitation of the shark skin’s mucus secretion, it is necessary to be further in-depth and improved to apply this antifouling agent into the marine antifouling field.
引文
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[2]张占平,齐育红,刘述锡等.大连水产学院学报[J].船舶防污涂料与防污剂的研究进展,2006,21,(2):175-179.
[3]桂泰江.仿生海洋防污涂料.中国涂料.2005,20(10):26-28.
[4]陈光宇.辣椒碱自抛光防污涂料及其制备方法[P].CN1296044A.2004.
[5]陈容发.海洋环保辣素防污漆[J].今日科技.2002,(2):12.
[6] Stupak M E.Garcia MT.Perez MC. Non-toxic Alternative Compounds for Marine Antifouling Paint [J]. International Biodeterioration and Biodegradation.2003, 52: 49-52.
[7] Yamashita N. etal. New Acrylated Rhaponticin Isolared from Eucalyptus Rubida as A Repellent Agaist The Blue Mussel Mytilus Edulis. Agric. Biol. Chem., 1989,53 (10):2827-829 .
[8] Hedo S. et al. Biosci.Biotech. Biochem. 1992, 56.
[9] Singh IP. et al.Potent Attachment–inhibiting and Promoting Substances for the Blue Mussel, Mytilus Edulis Galloprovincialia, from Two Species of Eucalyptus., Biotech. Biochem.1996,60 (9):1522~1523.
[10] Kon-ya.et al. Inhabitory Effect of Bacterial Ubiquinones on The Setting of Barnacle. Balnaus Amphitrite. Experientia .1995, 51:153-155.
[11] Todd JT.Zimmerman R C.Crews P.et al. The anti-fouling activity of natural and synthetic phenolic acid sulphate eaters.Phytochemistry.1993,34(2):401-404.
[12] Denys R. Stdnberg P. D. Willemsen P. et al. Broad spectrum effects of secondary metabolities from the red alga Deliseu pulchra in antifouling assays.Biofouling .1995 ,8:259～271.
[13] Sandy Morrison.Technology update: Antifouling coatings [J].Coatings and Inks.2005, 12.
[14] Goto R.Kado R.Muramoto K.et al.Furospongolide:an antifouling substance from the marine sponge Phyliospongia papyracea against the barnacle Balanus amphitrito[J].Nippon Suisan Gakkaishi.1993,59 :1953.
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