CN104031275A - Method for preparing clay modified polyvinyl alcohol antifouling hydrogel - Google Patents
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- 239000004927 clay Substances 0.000 title claims abstract description 59
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 51
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 50
- 239000000017 hydrogel Substances 0.000 title claims abstract description 35
- 230000003373 anti-fouling effect Effects 0.000 title abstract description 19
- 238000000034 method Methods 0.000 title abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000006185 dispersion Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 239000000499 gel Substances 0.000 claims description 21
- 239000010445 mica Substances 0.000 claims description 9
- 229910052618 mica group Inorganic materials 0.000 claims description 9
- 239000005995 Aluminium silicate Substances 0.000 claims description 7
- 235000012211 aluminium silicate Nutrition 0.000 claims description 7
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical class O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000012424 Freeze-thaw process Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000004075 alteration Effects 0.000 claims 12
- 150000004760 silicates Chemical class 0.000 claims 4
- 239000000463 material Substances 0.000 abstract description 7
- 241000195493 Cryptophyta Species 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 108090000623 proteins and genes Proteins 0.000 abstract description 4
- 102000004169 proteins and genes Human genes 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract 2
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 30
- 239000000243 solution Substances 0.000 description 12
- 239000002131 composite material Substances 0.000 description 7
- 238000012425 Freezing-thawing process Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000006136 alcoholysis reaction Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000440 bentonite Substances 0.000 description 3
- 229910000278 bentonite Inorganic materials 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 229920002554 vinyl polymer Polymers 0.000 description 1
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Abstract
Description
技术领域technical field
本发明涉及的是一种防污水凝胶的制备方法，尤其涉及一种机械性能良好的粘土改性聚乙烯醇防污水凝胶的制备方法。The invention relates to a preparation method of a sewage-repellent gel, in particular to a preparation method of a clay-modified polyvinyl alcohol-repellent sewage gel with good mechanical properties.
背景技术Background technique
海洋污损生物是指附着在船舶和海洋中其他设施表面的动物、植物和微生物的总称。这些细菌、藻类以及各种微生物、海洋动植物等生物在海洋设施表面附着、生长，这种现象就叫做生物污损。近年来，与海洋有关的行业(包括海水养殖、海底石油和海底矿产、海洋发电等)在迅速发展，人们开始越来越多的重视海洋生物污损现象，如何有效地防治海洋生物污损成为当今开发海洋产业首要解决的一个问题。Marine fouling organisms refer to the general term of animals, plants and microorganisms attached to the surface of ships and other facilities in the ocean. These bacteria, algae, various microorganisms, marine animals and plants adhere to and grow on the surface of marine facilities. This phenomenon is called biofouling. In recent years, marine-related industries (including mariculture, seabed oil and seabed minerals, marine power generation, etc.) have developed rapidly, and people have begun to pay more and more attention to marine biofouling. How to effectively prevent marine biofouling has become a One of the most important problems to be solved in the development of marine industry today.
传统的防污方法都是基于固体材料，较少人关注柔软的、湿润的材料，例如水凝胶。鲸鱼、海豚等海洋生物表面不易附着污染物，这是由于其表层明显为软的湿润的表面。在人类口腔黏膜内也发现了类似的防污行为。最近几年有关水凝胶的研究结果表明，水凝胶可在一定程度上抵抗蛋白质的吸附，并且以其较高的吸水率和无毒性吸引了世界各国的研究者，是一种潜在的高效且环保的新型海洋防污涂料。例如中国专利文件“一种脊状微结构表面的防污材料制备方法”(申请号201110162971.2)公开了一种在聚二甲基硅氧烷表面水解形成TiO2凝胶膜层，然后利用聚丙烯酸乙醇溶液与TiO2膜层进行自组装反应从而模拟鲨鱼表皮鳞片表面的脊状微结构，其防腐防污效果明显。又如中国专利文件“一种多孔水凝胶的制备方法及其应用”(申请号201210127397.1)公开了一种酰胺类改性聚乙烯醇多孔水凝胶的方法，将这种水凝胶放入海洋防污细菌培养液中达到溶胀平衡后放置在海洋环境中，在海洋污损生物生长旺季基本没有任何污损生物的附着。还有中国专利文件“一种常温固化防污减阻水凝胶软涂层的制备”(申请号201010549677.2)、“一种防污材料及其应用”(申请号201010589284.4)、“一种改性有机硅聚合物、制备方法及其应用”(申请号201210362472.2)等都是与防污水凝胶有关的技术，这些水凝胶防污材料虽然防污效果明显，但是原料价格昂贵、成本较高，制备过程复杂且水凝胶涂层机械性能差。Traditional antifouling methods are based on solid materials, and less attention has been paid to soft, wet materials such as hydrogels. The surface of marine organisms such as whales and dolphins is not easy to adhere to pollutants, because the surface layer is obviously soft and wet. Similar antifouling behavior has also been found in the human oral mucosa. Research results on hydrogels in recent years have shown that hydrogels can resist protein adsorption to a certain extent, and have attracted researchers from all over the world for their high water absorption and non-toxicity. And environmentally friendly new marine antifouling coatings. For example, the Chinese patent document "Preparation method of antifouling material on ridge microstructure surface" (application number 201110162971.2) discloses a TiO2 gel film layer formed on the surface of polydimethylsiloxane by hydrolysis, and then using polyacrylic acid The self-assembly reaction between the ethanol solution and the TiO 2 film layer simulates the ridge-like microstructure on the surface of the shark's epidermal scales, and its anti-corrosion and anti-fouling effect is obvious. Another example is the Chinese patent document "Preparation Method and Application of a Porous Hydrogel" (Application No. 201210127397.1) which discloses a method for amide-modified polyvinyl alcohol porous hydrogel. After the marine antifouling bacteria culture solution reaches the swelling equilibrium and is placed in the marine environment, there is basically no attachment of any fouling organisms during the peak growth season of marine fouling organisms. There are also Chinese patent documents "Preparation of a normal temperature curing antifouling and drag reducing hydrogel soft coating" (application number 201010549677.2), "an antifouling material and its application" (application number 201010589284.4), "a modified Silicone polymers, preparation methods and applications" (application number 201210362472.2) are all technologies related to antifouling gels. Although these hydrogel antifouling materials have obvious antifouling effects, the raw materials are expensive and costly. The preparation process is complicated and the mechanical properties of the hydrogel coating are poor.
发明内容Contents of the invention
本发明的目的在于提供一种工艺简单，原料易于得到且制备成本低廉，所得凝胶体系防污效果优良的粘土改性聚乙烯醇防污水凝胶的制备方法。The object of the present invention is to provide a preparation method of clay-modified polyvinyl alcohol anti-sewage gel with simple process, easy-to-obtain raw materials and low preparation cost, and excellent anti-fouling effect of the obtained gel system.
本发明的目的是这样实现的：The purpose of the present invention is achieved like this:
(1)将无机粘土加热溶于去离子水中，充分溶解得到悬浮液，然后将该悬浮液超声分散，得到均匀的粘土分散液；(1) heating and dissolving the inorganic clay in deionized water, fully dissolving to obtain a suspension, and then ultrasonically dispersing the suspension to obtain a uniform clay dispersion;
(2)向粘土分散液中加入聚乙烯醇，80～100℃下搅拌2～3h，得到粘土改性聚乙烯醇水凝胶混合溶液；(2) adding polyvinyl alcohol to the clay dispersion, and stirring at 80-100°C for 2-3 hours to obtain a clay-modified polyvinyl alcohol hydrogel mixed solution;
(3)将粘土改性聚乙烯醇水凝胶混合溶液重复至少三次冷冻-解冻过程，制得粘土改性聚乙烯醇防污水凝胶。(3) Repeat the freezing-thawing process at least three times for the clay-modified polyvinyl alcohol hydrogel mixed solution to prepare the clay-modified polyvinyl alcohol anti-sewage gel.
本发明还可以包括：The present invention may also include:
1、所述将无机粘土加热溶于去离子水中，无机粘土的用量的比例为0.5～4.0g/100mL水。1. The inorganic clay is heated and dissolved in deionized water, and the ratio of the amount of the inorganic clay is 0.5-4.0g/100mL water.
2、所述向粘土分散液中加入聚乙烯醇，聚乙烯醇的用量为5～10g/100mL水。2. Adding polyvinyl alcohol to the clay dispersion, the amount of polyvinyl alcohol is 5-10g/100mL water.
3、所述冷冻-解冻过程中，冷冻温度为-20℃，解冻温度为20℃。3. During the freezing-thawing process, the freezing temperature is -20°C, and the thawing temperature is 20°C.
4、所述无机粘土为膨润土、高岭土以及云母无机层状硅酸盐粘土类中的至少一种。4. The inorganic clay is at least one of bentonite, kaolin and mica inorganic layered silicate clay.
5、所述聚乙烯醇的聚合度为500～3000，醇解度为50％～90％。所述聚乙烯醇采用的规格为1788、1795、1799或2099的聚乙烯醇中的一种或者多种任意混合。5. The degree of polymerization of the polyvinyl alcohol is 500-3000, and the degree of alcoholysis is 50%-90%. One or more polyvinyl alcohols with specifications of 1788, 1795, 1799 or 2099 used for the polyvinyl alcohol are mixed arbitrarily.
本发明的方法制备的防污水凝胶网络结构均匀，适量的粘土在凝胶体系中充当物理交联点，从而增强水凝胶体系的机械强度。本方法制备工艺简单，原料易于得到且制备成本低廉。所得凝胶体系防污效果优良，可有效抑制蛋白及海洋藻类的附着，在船舶防污材料领域具有很好的应用前景。The anti-sewage gel network structure prepared by the method of the invention is uniform, and an appropriate amount of clay acts as a physical cross-linking point in the gel system, thereby enhancing the mechanical strength of the hydrogel system. The preparation process of the method is simple, the raw materials are easy to obtain and the preparation cost is low. The obtained gel system has excellent antifouling effect, can effectively inhibit the attachment of proteins and marine algae, and has good application prospects in the field of ship antifouling materials.
本发明的有益效果在于：本发明采用表面带有大量羟基的聚乙烯醇为基底材料，添加价格比较低廉并且易得的层状硅酸盐粘土，用去离子水为溶剂，经冷冻解冻数次物理交联，最终制得机械性能优异的防污水凝胶。选取的这类粘土其层间靠范德华作用相结合，作用力比较弱，很容易形成稳定的悬浮液，当其加入到聚乙烯醇水凝胶基质中后，会起到一定的物理交联点的作用，从而使得复合体系的机械性能得到增强。该发明操作工艺简单、成本低廉，所制得的防污水凝胶具有良好的机械性能以及抗海藻附着及抗蛋白吸附的性能。The beneficial effects of the present invention are: the present invention uses polyvinyl alcohol with a large number of hydroxyl groups on the surface as the base material, adds relatively cheap and easily available layered silicate clay, uses deionized water as the solvent, and freezes and thaws several times Physically cross-linked to finally obtain a sewage-repellent gel with excellent mechanical properties. The selected clay layer is combined by van der Waals effect, the force is relatively weak, and it is easy to form a stable suspension. When it is added to the polyvinyl alcohol hydrogel matrix, it will play a certain physical cross-linking point The role, so that the mechanical properties of the composite system is enhanced. The invention has simple operation process and low cost, and the prepared anti-sewage gel has good mechanical properties and anti-algae adhesion and anti-protein adsorption properties.
附图说明Description of drawings
图1为膨润土添加量为1.0％的改性聚乙烯醇水凝胶的SEM图。Figure 1 is a SEM image of a modified polyvinyl alcohol hydrogel with a bentonite addition of 1.0%.
图2为不同粘土含量的改性聚乙烯醇水凝胶的蛋白质吸附。Figure 2 shows the protein adsorption of modified polyvinyl alcohol hydrogels with different clay contents.
图3为云母添加量为2.0％的改性聚乙烯醇水凝胶表面海藻的附着情况。Figure 3 shows the adhesion of algae on the surface of the modified polyvinyl alcohol hydrogel with the addition of 2.0% mica.
具体实施方式Detailed ways
为了使本发明的目的、技术方案和优点更加清楚，下面对本发明的具体实施进行详述。In order to make the purpose, technical solution and advantages of the present invention clearer, the specific implementation of the present invention will be described in detail below.
实施例1：称取膨润土4份(占整个复合水凝胶体系的质量百分数)，定量加到水溶液中，使粘土在溶液中分散均匀，然后加入聚乙烯醇10份，使其充分溶解，通过物理交联法制备粘土改性聚乙烯醇水凝胶。Embodiment 1: take by weighing 4 parts of bentonite (accounting for the mass percent of whole composite hydrogel system), quantitatively add in the aqueous solution, make the clay disperse evenly in the solution, then add 10 parts of polyvinyl alcohol, make it fully dissolve, pass Preparation of clay-modified polyvinyl alcohol hydrogel by physical cross-linking method.
实施例2：称取高岭土4份(占整个复合水凝胶体系的质量百分数)，定量加到水溶液中，使粘土在溶液中分散均匀，然后加入聚乙烯醇10份，使其充分溶解，重复三次冷冻-解冻过程制得粘土改性聚乙烯醇水凝胶。Embodiment 2: take by weighing 4 parts of kaolin (accounting for the mass percent of whole composite hydrogel system), quantitatively add in the aqueous solution, make the clay disperse evenly in the solution, then add 10 parts of polyvinyl alcohol, make it fully dissolve, repeat Clay-modified polyvinyl alcohol hydrogels were prepared through three freeze-thaw processes.
实施例3：称取高岭土4份(占整个复合水凝胶体系的质量百分数)，定量加到水溶液中，室温下磁力搅拌2h，得到粘土分散液，然后将该悬浮液超声20min，使粘土在溶液中分散均匀，然后加入聚合度为1750，醇解度为50％的聚乙烯醇，搅拌3h，使其充分溶解，重复三次冷冻-解冻过程制得粘土改性聚乙烯醇水凝胶。Embodiment 3: Weigh 4 parts of kaolin (accounting for the mass percentage of the whole composite hydrogel system), quantitatively add to the aqueous solution, and magnetically stir at room temperature for 2 hours to obtain a clay dispersion, and then ultrasonically 20min the suspension to make the clay in Disperse evenly in the solution, then add polyvinyl alcohol with a degree of polymerization of 1750 and a degree of alcoholysis of 50%, stir for 3 hours to fully dissolve, and repeat the freezing-thawing process three times to obtain a clay-modified polyvinyl alcohol hydrogel.
实施例4：称取云母4份(占整个复合水凝胶体系的质量百分数)，定量加到水溶液中，室温下磁力搅拌2h，得到粘土分散液，然后将该悬浮液超声20min，使粘土在溶液中分散均匀，用油浴锅加热溶液至90℃，加入聚合度为1750，醇解度为50％的聚乙烯醇，搅拌3h，使其充分溶解，重复三次冷冻-解冻过程制得粘土改性聚乙烯醇水凝胶。Example 4: Weigh 4 parts of mica (accounting for the mass percent of the entire composite hydrogel system), quantitatively add it to the aqueous solution, and magnetically stir it at room temperature for 2 hours to obtain a clay dispersion, and then ultrasonicate the suspension for 20 minutes to make the clay in Disperse evenly in the solution, heat the solution to 90°C with an oil bath, add polyvinyl alcohol with a degree of polymerization of 1750 and a degree of alcoholysis of 50%, stir for 3 hours to fully dissolve it, and repeat the freezing-thawing process three times to obtain a modified clay permanent polyvinyl alcohol hydrogel.
实施例5：称取云母4份(占整个复合水凝胶体系的质量百分数)，定量加到水溶液中，室温下磁力搅拌2h，得到粘土分散液，然后将该悬浮液超声20min，使粘土在溶液中分散均匀，用油浴锅加热溶液至90℃，加入聚合度为1750，醇解度为50％的聚乙烯醇，搅拌3h，使其充分溶解，将粘土与聚乙烯醇的混合溶液一部分倒入培养皿中浇注成片，另一部分倒入离心管中浇注成柱，重复三次冷冻-解冻过程制得粘土改性聚乙烯醇水凝胶。Example 5: Weigh 4 parts of mica (accounting for the mass percent of the entire composite hydrogel system), quantitatively add it to the aqueous solution, and stir magnetically at room temperature for 2 hours to obtain a clay dispersion, and then ultrasonically 20 minutes the suspension to make the clay Disperse evenly in the solution, heat the solution to 90°C with an oil bath, add polyvinyl alcohol with a degree of polymerization of 1750 and a degree of alcoholysis of 50%, stir for 3 hours to fully dissolve, and mix a part of the mixed solution of clay and polyvinyl alcohol Pour it into a petri dish to form a sheet, and pour the other part into a centrifuge tube to form a column. Repeat the freezing-thawing process three times to prepare the clay-modified polyvinyl alcohol hydrogel.
实施例6：称取云母4份(占整个复合水凝胶体系的质量百分数)，定量加到水溶液中，室温下磁力搅拌2h，得到粘土分散液，然后将该悬浮液超声20min，使粘土在溶液中分散均匀，用油浴锅加热溶液至90℃，加入聚合度为1750，醇解度为50％的聚乙烯醇，搅拌3h，使其充分溶解，将粘土与聚乙烯醇的混合溶液一部分倒入培养皿中浇注成片，另一部分倒入离心管中浇注成柱，将样品放置-20℃下冷冻12h，然后放置20℃下解冻12h。重复三次冷冻-解冻过程制得粘土改性聚乙烯醇水凝胶。Example 6: Weigh 4 parts of mica (accounting for the mass percent of the entire composite hydrogel system), quantitatively add to the aqueous solution, and magnetically stir for 2 hours at room temperature to obtain a clay dispersion, and then ultrasonically 20 minutes the suspension to make the clay in Disperse evenly in the solution, heat the solution to 90°C with an oil bath, add polyvinyl alcohol with a degree of polymerization of 1750 and a degree of alcoholysis of 50%, stir for 3 hours to fully dissolve, and mix a part of the mixed solution of clay and polyvinyl alcohol Pour it into a Petri dish and cast it into a sheet, and pour the other part into a centrifuge tube to cast it into a column. The sample is frozen at -20°C for 12 hours, and then thawed at 20°C for 12 hours. The clay-modified polyvinyl alcohol hydrogel was prepared by repeating the freezing-thawing process three times.
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