本文選題：DBD等離子體炬 + 等離子體聚合　； 參考：《浙江理工大學(xué)》2017年碩士論文

【摘要】：BOPP(雙向拉伸聚丙烯)薄膜材料由于具有無色、無味、無毒、高拉伸強(qiáng)度、沖擊強(qiáng)度、強(qiáng)韌性及良好的透明性等優(yōu)異性能,在包裝和印刷領(lǐng)域已得到廣泛應(yīng)用。但是BOPP薄膜的表面能較低,比如BOPP表面無法印刷水性油墨及其生物相容性差等缺陷,阻礙了其在某些領(lǐng)域的應(yīng)用深度。因此改善BOPP薄膜材料的表面親水性能,實(shí)現(xiàn)BOPP材料的功能化是高分子薄膜材料領(lǐng)域的一個(gè)重要研究內(nèi)容。低溫等離子體技術(shù)對材料表面改性因不會(huì)對基體造成損傷,無需化學(xué)溶劑、干法改性等優(yōu)勢,在高分子材料表面改性方面得到廣泛應(yīng)用。但是傳統(tǒng)低溫等離子體需要昂貴的真空系統(tǒng),無法應(yīng)用在低附加值薄膜改性。此外,等離子體表面處理的時(shí)效性也限制了其在薄膜改性領(lǐng)域的應(yīng)用廣度。在本論文中,我們創(chuàng)新性的使用了大氣壓等離子體聚合改性及等離子體涂覆改性模式,實(shí)現(xiàn)了BOPP薄膜表面永久改性,有望在環(huán)保印刷和包裝領(lǐng)域得到廣泛應(yīng)用。為了使BOPP薄膜達(dá)到親水改性的目的,我們利用方法1:DBD等離子體對BOPP薄膜進(jìn)行預(yù)處理,然后經(jīng)混合涂層(PVA/SF/PEG)進(jìn)行涂覆,最后經(jīng)乙醇固化來對BOPP薄膜實(shí)現(xiàn)永久親水改性的目的,并對改性后的BOPP薄膜進(jìn)行親水性探究和對水性油墨印刷效果的測試;方法2:通過Ar/O_2和He/O_2氣氛的等離子體炬在BOPP薄膜材料表面聚合丙烯胺單體,探究聚合改性BOPP薄膜生物相容性。利用大氣壓介質(zhì)阻擋放電等離子對BOPP薄膜表面進(jìn)行預(yù)處理,在其表面成功引入了-COOH、-OH等極性官能團(tuán),大大提高了BOPP薄膜與表面改性混合涂層(聚乙烯醇/絲素溶液/聚乙二醇,即PVA/SF/PEG)之間的界面結(jié)合力,促進(jìn)了改性涂層的穩(wěn)定性。此外發(fā)現(xiàn),BOPP薄膜經(jīng)過DBD等離子體預(yù)處理后,其拉伸性能和光學(xué)性能基本保持原薄膜的優(yōu)良性能。進(jìn)一步經(jīng)混合涂層進(jìn)行涂覆后,經(jīng)紅外和接觸角分析可知,O-C、N-C等官能團(tuán)成功接枝在BOPP薄膜的表面上,表面自由能得到了明顯的提高,改性BOPP接觸角從105°降低到20°。混合涂層中加入絲素蛋白溶液(SF),涂覆后經(jīng)60%乙醇處理后,絲素蛋白溶液由α螺旋到β折疊從而發(fā)生結(jié)構(gòu)的轉(zhuǎn)變,絲素蛋白加入使得BOPP薄膜表面的透光率達(dá)到幾乎100%,混合涂層中的PEG,可以使BOPP薄膜表面具有更好的粘結(jié)作用和柔軟特性。另一種是通過惰性氣體等離子體炬聚合丙烯胺改性BOPP薄膜表面親水性的方法,當(dāng)惰性氣體流量為0.4 m~3·h~(-1)、O_2氣體流量為0.1 m~3·h~(-1)時(shí),Ar等離子體炬的聚合速率約為200nm·min~(-1),而He等離子體炬的聚合速率約為40 nm·min~(-1)。同時(shí),Ar等離子體炬沉積的丙烯胺聚合物薄膜的耐水性要優(yōu)于He等離子體炬。等離子體炬沉積的丙烯胺聚合物薄膜是由大量的納米結(jié)點(diǎn)組成,而聚合物薄膜納米結(jié)點(diǎn)的尺寸大小和密度受放電氣體種類(Ar/O_2或He/O_2)、載氣氣體流量等因素影響。在相同條件下,經(jīng)Ar/O_2/ALA等離子體炬聚合改性后的BOPP薄膜表面上C-N/C=N和N-C=O/C=O鍵含量分別為14.5%和17.3%,這些值均高于由He/O_2/ALA等離子體處理的樣品值,達(dá)到約2.8和1.7倍。這種研究結(jié)果歸因于Ar/O_2等離子體具有較高的離子密度會(huì)產(chǎn)生較高的ALA濃度,導(dǎo)致較高密度的羰基官能團(tuán)被接枝到BOPP薄膜的表面上。細(xì)胞毒性及粘附實(shí)驗(yàn)分析發(fā)現(xiàn),BOPP表面經(jīng)改性后有大量的細(xì)胞粘附在其表面上,其中Ar/O_2/ALA等離子體炬聚合改性后粘附的細(xì)胞數(shù)量比He/O_2/ALA等離子體炬約多1.5×105/mm~2。這不僅克服了原有BOPP薄膜粘附性較弱的問題,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.
【學(xué)位授予單位】：浙江理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TS802;TB484

【參考文獻(xiàn)】

相關(guān)期刊論文 前1條

1 陳光良;鄭旭;黃俊;司曉蕾;陳致力;薛飛;Sylvain Massey;;Three different low-temperature plasma-based methods for hydrophilicity improvement of polyethylene films at atmospheric pressure[J];Chinese Physics B;2013年11期

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本文編號：1972790