气相法高分子薄膜的纳米尺度调控和功能化
发布时间：2018-10-24 19:42
【摘要】：功能高分子薄膜作为一种表界面材料在生产生活中具有重要的应用价值,随着制备方法和工艺的逐渐成熟,研究重点逐渐向提高薄膜的稳定性和功能最大化方向发展。本文主要研究了引发式化学气相沉积方法制备功能高分子薄膜,探索了纳米尺度调控对薄膜结构和功能的优化,制备了亲水、超亲水表面和结构化超疏水、超疏油表面,以及对不同性质表面的应用做了初步探索。具体研究内容和成果如下:1.亲水抗生物吸附聚乙烯基吡咯烷酮(poly(N-vinyl pyrrolidone),PVP)薄膜,采用丙烯酸乙二醇酯(EGDA)作为交联剂,通过控制单体流量比得到了不同交联度的聚乙烯基吡咯烷酮-丙烯酸乙二醇酯共聚物薄膜(P(VP-co-EGDA))。对于平面和非平面基底分别采用直接接枝和分层原位接枝的方法提高薄膜与基底的结合强度。薄膜的亲水性以及抗生物吸附性随着交联度的减小而增加,平面基底和非平面基底最小水接触角分别为33±1o和0o。亲水改性的聚偏氟乙烯滤膜对蛋白质的吸附最佳效果减少了92%,并且能够有效减少大肠杆菌的吸附。直接接枝和双层原位接枝两种薄膜经长期水洗和超声处理后都能保持结构和功能的稳定性。2.我们在P(VP-co-EGDA)薄膜生长过程中原位接枝PVP,进一步提高了薄膜的亲水性与生物相容性。XPS测试结果表明,接枝PVP后相比于交联度最低的P(VP-co-EGDA)表面N元素的含量增加37%,表明内酰胺基团数量大大增加。水接触角测试结果中,接枝PVP的表面接触角进一步减小了11o。我们分别采用P(VP-co-EGDA)和P(VP-co-EGDA)基础上原位复合接枝PVP的薄膜对医用导管进行亲水改性,改性后导管水接触角分别为38o和28o。然后将这两种薄膜改性的导管植入小鼠皮下进行生物相容性测试,结果表明改性的导管相比未改性的导管生物相容性都有提高,其中经过原位接枝PVP的导管生物组织相容性效果更佳。3.气相法单步制备聚合物纳米阵列。在全氟癸基丙烯酸酯(PFDA)沉积过程中引入EGDA促使PPFDA纳米阵列结构的形成,通过调节EGDA和PFDA分压得到了不同密度和形貌的PPFDA纳米锥阵列,结构尺寸随着沉积时间的增加而增加。这种有序的PPFDA纳米锥阵列的形成具有基底普适性,由于全氟侧链极低的表面能和纳米粗糙度赋予了表面超疏水、超疏油的特性,其中在棉布表面水、甘油、乙二醇、二碘甲烷、菜油接触角均在170o以上,辛烷接触角在150o以上;纳米阵列修饰的硅片表面接触角前进角为162o,后退角为158o,滑动角小于1o。这种气相构筑聚合物纳米阵列的研究成果在制备超疏水超疏油表面以及聚合物纳米结构化生长方面均具有突破性的意义。本文通过以上三个部分的工作探索了气相法纳米尺度调控对薄膜稳定性、功能性以及表面结构化的影响和作用,为制备不同功能性的高分子薄膜提供了新的思路。
[Abstract]:As a kind of surface interface material, functional polymer film has important application value in production and life. With the maturation of preparation method and technology, the research focus is to improve the stability and function maximization of the film. In this paper, the preparation of functional polymer thin films by initiator chemical vapor deposition was studied. The structure and function of the films were optimized by nano-scale control. The hydrophilic, super-hydrophilic and structured super-hydrophobic and super-hydrophobic surfaces were prepared. As well as the application of different surface properties have been preliminarily explored. The specific research contents and results are as follows: 1. Hydrophilic and bioadsorbed polyvinylpyrrolidone (poly (N-vinyl pyrrolidone), PVP) thin films were prepared by using ethylene glycol acrylate (EGDA) as crosslinking agent. The poly (vinylpyrrolidone) acrylate copolymer (P (VP-co-EGDA).) film with different crosslinking degree was obtained by controlling the monomer flow ratio. For planar and non-planar substrates, direct grafting and delamination in situ grafting were used to improve the bonding strength between the films and the substrates, respectively. The hydrophilicity and bioabsorbability of the films increase with the decrease of cross-linking degree. The minimum water contact angles of planar and non-planar substrates are 33 卤1o and 0o. respectively. The hydrophilic modified polyvinylidene fluoride filter membrane can reduce the adsorption of protein by 922%, and can effectively reduce the adsorption of Escherichia coli. Direct grafting and double in-situ grafting can keep the stability of structure and function after long-term washing and ultrasonic treatment. 2. During the growth of P (VP-co-EGDA) films, we further improved the hydrophilicity and biocompatibility of P (VP-co-EGDA) films by in-situ grafting of PVP,. Compared with P (VP-co-EGDA) with the lowest crosslinking degree, the N element content of grafted PVP increased by 37%, indicating that the number of lactam groups increased greatly. The surface contact angle of grafted PVP was further decreased by 11o. The hydrophilic modification of medical catheter was carried out by using in situ composite grafted PVP films on the basis of P (VP-co-EGDA) and P (VP-co-EGDA), respectively. The water contact angles of the modified conduits were 38 o and 28 o, respectively. Then the two kinds of thin-film modified catheters were implanted into mice subcutaneously for biocompatibility test. The results showed that the biocompatibility of the modified ducts was better than that of the unmodified ducts. Among them, the biocompatibility of ducts grafted with PVP in situ was better. 3. 3. Polymer nanoarrays were prepared by gas phase method. During the deposition of perfluorodecyl acrylate (PFDA), EGDA was introduced to promote the formation of PPFDA nanoarrays. By adjusting the partial pressure of EGDA and PFDA, different density and morphologies of PPFDA nanoconical arrays were obtained, and the structure size increased with the increase of deposition time. The formation of this ordered PPFDA nanoconical array has the universality of substrate. Due to the extremely low surface energy and nanometer roughness of perfluorinated side chain, the surface is superhydrophobic and super-oil-thinning, in which water, glycerol, ethylene glycol, diiodomethane are found on the surface of cotton cloth. The contact angle of rapeseed oil is more than 170 o and the contact angle of octane is more than 150 o. The surface contact angle of nano-array modified silicon wafer is 162o. the angle of receding is 158o. the angle of sliding is less than 1o. The results of gas phase fabrication of polymer nanoarrays are of great significance in the preparation of superhydrophobic surfaces and in the preparation of polymer nanostructured growth. Through the work of the above three parts, this paper explores the effect and effect of nanometer scale control of gas phase method on the stability, functionality and surface structure of the films, which provides a new way of thinking for the preparation of different functional polymer thin films.
【学位授予单位】：宁波大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB383.2;TQ317
本文编号：2292369
[Abstract]:As a kind of surface interface material, functional polymer film has important application value in production and life. With the maturation of preparation method and technology, the research focus is to improve the stability and function maximization of the film. In this paper, the preparation of functional polymer thin films by initiator chemical vapor deposition was studied. The structure and function of the films were optimized by nano-scale control. The hydrophilic, super-hydrophilic and structured super-hydrophobic and super-hydrophobic surfaces were prepared. As well as the application of different surface properties have been preliminarily explored. The specific research contents and results are as follows: 1. Hydrophilic and bioadsorbed polyvinylpyrrolidone (poly (N-vinyl pyrrolidone), PVP) thin films were prepared by using ethylene glycol acrylate (EGDA) as crosslinking agent. The poly (vinylpyrrolidone) acrylate copolymer (P (VP-co-EGDA).) film with different crosslinking degree was obtained by controlling the monomer flow ratio. For planar and non-planar substrates, direct grafting and delamination in situ grafting were used to improve the bonding strength between the films and the substrates, respectively. The hydrophilicity and bioabsorbability of the films increase with the decrease of cross-linking degree. The minimum water contact angles of planar and non-planar substrates are 33 卤1o and 0o. respectively. The hydrophilic modified polyvinylidene fluoride filter membrane can reduce the adsorption of protein by 922%, and can effectively reduce the adsorption of Escherichia coli. Direct grafting and double in-situ grafting can keep the stability of structure and function after long-term washing and ultrasonic treatment. 2. During the growth of P (VP-co-EGDA) films, we further improved the hydrophilicity and biocompatibility of P (VP-co-EGDA) films by in-situ grafting of PVP,. Compared with P (VP-co-EGDA) with the lowest crosslinking degree, the N element content of grafted PVP increased by 37%, indicating that the number of lactam groups increased greatly. The surface contact angle of grafted PVP was further decreased by 11o. The hydrophilic modification of medical catheter was carried out by using in situ composite grafted PVP films on the basis of P (VP-co-EGDA) and P (VP-co-EGDA), respectively. The water contact angles of the modified conduits were 38 o and 28 o, respectively. Then the two kinds of thin-film modified catheters were implanted into mice subcutaneously for biocompatibility test. The results showed that the biocompatibility of the modified ducts was better than that of the unmodified ducts. Among them, the biocompatibility of ducts grafted with PVP in situ was better. 3. 3. Polymer nanoarrays were prepared by gas phase method. During the deposition of perfluorodecyl acrylate (PFDA), EGDA was introduced to promote the formation of PPFDA nanoarrays. By adjusting the partial pressure of EGDA and PFDA, different density and morphologies of PPFDA nanoconical arrays were obtained, and the structure size increased with the increase of deposition time. The formation of this ordered PPFDA nanoconical array has the universality of substrate. Due to the extremely low surface energy and nanometer roughness of perfluorinated side chain, the surface is superhydrophobic and super-oil-thinning, in which water, glycerol, ethylene glycol, diiodomethane are found on the surface of cotton cloth. The contact angle of rapeseed oil is more than 170 o and the contact angle of octane is more than 150 o. The surface contact angle of nano-array modified silicon wafer is 162o. the angle of receding is 158o. the angle of sliding is less than 1o. The results of gas phase fabrication of polymer nanoarrays are of great significance in the preparation of superhydrophobic surfaces and in the preparation of polymer nanostructured growth. Through the work of the above three parts, this paper explores the effect and effect of nanometer scale control of gas phase method on the stability, functionality and surface structure of the films, which provides a new way of thinking for the preparation of different functional polymer thin films.
【学位授予单位】：宁波大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB383.2;TQ317
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