大气压等离子体对BOPP薄膜表面结构调控研究

发布时间：2018-06-03 12:32

本文选题：DBD等离子体炬 + 等离子体聚合　；参考：《浙江理工大学》2017年硕士论文

【摘要】：BOPP(双向拉伸聚丙烯)薄膜材料由于具有无色、无味、无毒、高拉伸强度、冲击强度、强韧性及良好的透明性等优异性能,在包装和印刷领域已得到广泛应用。但是BOPP薄膜的表面能较低,比如BOPP表面无法印刷水性油墨及其生物相容性差等缺陷,阻碍了其在某些领域的应用深度。因此改善BOPP薄膜材料的表面亲水性能,实现BOPP材料的功能化是高分子薄膜材料领域的一个重要研究内容。低温等离子体技术对材料表面改性因不会对基体造成损伤,无需化学溶剂、干法改性等优势,在高分子材料表面改性方面得到广泛应用。但是传统低温等离子体需要昂贵的真空系统,无法应用在低附加值薄膜改性。此外,等离子体表面处理的时效性也限制了其在薄膜改性领域的应用广度。在本论文中,我们创新性的使用了大气压等离子体聚合改性及等离子体涂覆改性模式,实现了BOPP薄膜表面永久改性,有望在环保印刷和包装领域得到广泛应用。为了使BOPP薄膜达到亲水改性的目的,我们利用方法1:DBD等离子体对BOPP薄膜进行预处理,然后经混合涂层(PVA/SF/PEG)进行涂覆,最后经乙醇固化来对BOPP薄膜实现永久亲水改性的目的,并对改性后的BOPP薄膜进行亲水性探究和对水性油墨印刷效果的测试;方法2:通过Ar/O_2和He/O_2气氛的等离子体炬在BOPP薄膜材料表面聚合丙烯胺单体,探究聚合改性BOPP薄膜生物相容性。利用大气压介质阻挡放电等离子对BOPP薄膜表面进行预处理,在其表面成功引入了-COOH、-OH等极性官能团,大大提高了BOPP薄膜与表面改性混合涂层(聚乙烯醇/丝素溶液/聚乙二醇,即PVA/SF/PEG)之间的界面结合力,促进了改性涂层的稳定性。此外发现,BOPP薄膜经过DBD等离子体预处理后,其拉伸性能和光学性能基本保持原薄膜的优良性能。进一步经混合涂层进行涂覆后,经红外和接触角分析可知,O-C、N-C等官能团成功接枝在BOPP薄膜的表面上,表面自由能得到了明显的提高,改性BOPP接触角从105°降低到20°。混合涂层中加入丝素蛋白溶液(SF),涂覆后经60%乙醇处理后,丝素蛋白溶液由α螺旋到β折叠从而发生结构的转变,丝素蛋白加入使得BOPP薄膜表面的透光率达到几乎100%,混合涂层中的PEG,可以使BOPP薄膜表面具有更好的粘结作用和柔软特性。另一种是通过惰性气体等离子体炬聚合丙烯胺改性BOPP薄膜表面亲水性的方法,当惰性气体流量为0.4 m~3·h~(-1)、O_2气体流量为0.1 m~3·h~(-1)时,Ar等离子体炬的聚合速率约为200nm·min~(-1),而He等离子体炬的聚合速率约为40 nm·min~(-1)。同时,Ar等离子体炬沉积的丙烯胺聚合物薄膜的耐水性要优于He等离子体炬。等离子体炬沉积的丙烯胺聚合物薄膜是由大量的纳米结点组成,而聚合物薄膜纳米结点的尺寸大小和密度受放电气体种类(Ar/O_2或He/O_2)、载气气体流量等因素影响。在相同条件下,经Ar/O_2/ALA等离子体炬聚合改性后的BOPP薄膜表面上C-N/C=N和N-C=O/C=O键含量分别为14.5%和17.3%,这些值均高于由He/O_2/ALA等离子体处理的样品值,达到约2.8和1.7倍。这种研究结果归因于Ar/O_2等离子体具有较高的离子密度会产生较高的ALA浓度,导致较高密度的羰基官能团被接枝到BOPP薄膜的表面上。细胞毒性及粘附实验分析发现,BOPP表面经改性后有大量的细胞粘附在其表面上,其中Ar/O_2/ALA等离子体炬聚合改性后粘附的细胞数量比He/O_2/ALA等离子体炬约多1.5×105/mm~2。这不仅克服了原有BOPP薄膜粘附性较弱的问题,而且提高了其生物相容性。
[Abstract]:BOPP (biaxially stretched polypropylene) film materials have been widely used in packaging and printing because of their colorless, tasteless, non-toxic, non-toxic, high tensile strength, impact strength, strength and toughness and good transparency. But the surface energy of BOPP films is low, such as the lack of printed water-based ink on the surface of BOPP and the poor biocompatibility. Therefore, the improvement of the surface hydrophilicity of BOPP film materials and the realization of the functionalization of BOPP materials are an important research content in the field of polymer film materials. The surface modification of the materials by low temperature plasma technology will not cause damage to the substrate, no chemical solvent, dry modification and so on. It is widely used in the surface modification of polymer materials. However, the traditional low temperature plasma needs an expensive vacuum system and can not be used in the low added value film modification. In addition, the aging of the plasma surface treatment also restricts its application in the field of film modification. In this paper, we use the atmosphere innovatively. The permanent modification of BOPP film surface has been achieved by plasma polymerization modification and plasma coating modification. It is expected to be widely used in the field of environmental protection printing and packaging. In order to achieve the purpose of hydrophilic modification of BOPP thin films, we pretreated the BOPP film by means of 1:DBD plasma and then mixed coating (PVA/SF/PEG). After coating, the purpose of permanent hydrophilic modification of BOPP film was achieved by ethanol curing, and the hydrophilicity of the modified BOPP film was explored and the printing effect of water-based ink was tested. Method 2: was used to polymerize the amines on the surface of BOPP film material through the plasma torch of Ar/O_2 and He/O_2 atmosphere, and to explore the polymerization of the modified BOPP thin. Membrane biocompatibility. The surface of BOPP film was pretreated with atmospheric pressure dielectric barrier discharge plasma. -COOH, -OH and other polar functional groups were successfully introduced on its surface, which greatly improved the interfacial bonding force between the BOPP film and the surface modified mixed coating (polyvinyl alcohol / silk fibroin / polyethylene glycol, PVA/SF/PEG), and promoted the modification. It is found that the tensile and optical properties of the BOPP film are basically maintained by the DBD plasma pretreatment. After the coating is further coated, the infrared and contact angle analysis shows that the functional groups such as O-C, N-C and other functional groups succeed to the surface of the BOPP film, and the free energy of the surface can be obtained. The contact angle of the modified BOPP decreased from 105 to 20. The mixed coating was added with the silk fibroin solution (SF). After the coating was treated with 60% ethanol, the silk fibroin solution was transformed from alpha helix to beta, and the light transmittance of the surface of the BOPP film was almost 100%, and the PEG in the mixed coating could be obtained. The surface of BOPP film has better adhesion and softness. The other is to modify the surface hydrophilicity of BOPP film by an inert gas plasma torch. When the inert gas flow is 0.4 m~3. H~ (-1), and the flow rate of O_2 is 0.1 m~3. H~ (-1), the polymerization rate of Ar plasma torch is about 200nm min~. The polymerization rate of the plasma torch is about 40 nm. Min~ (-1). At the same time, the water resistance of the amines deposited by the Ar plasma torch is better than that of the He plasma torch. The amines deposited by the plasma torch are made up of a large number of nanoscale nodes, and the size and density of the polymer thin film nanoscale are affected by the discharge gas. Under the same conditions, the content of C-N/C=N and N-C=O/C=O bonds on the surface of BOPP films modified by Ar/O_2/ALA plasma torch is 14.5% and 17.3% respectively under the same conditions. These values are all higher than the values of the samples treated by the He/O_2/ALA plasma, reaching about 2.8 and 1.7 times. The results are attributed to the results of this study. The high density of the Ar/O_2 plasma produces higher ALA concentration, resulting in the grafting of higher density carbonyl functional groups on the surface of the BOPP film. Cytotoxicity and adhesion experimental analysis found that a large number of cells adhered to the surface of the BOPP surface after modification, and the Ar/O_2/ALA plasma torch was modified after the polymerization of the plasma torch. The number of cells adhering to the He/O_2/ALA plasma torch is about 1.5 x 105/mm~2., which not only overcomes the weak adhesion of the original BOPP film, but also improves its biocompatibility.
【学位授予单位】：浙江理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TS802;TB484

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