氣相法高分子薄膜的納米尺度調(diào)控和功能化
發(fā)布時(shí)間：2018-10-24 19:42
【摘要】：功能高分子薄膜作為一種表界面材料在生產(chǎn)生活中具有重要的應(yīng)用價(jià)值,隨著制備方法和工藝的逐漸成熟,研究重點(diǎn)逐漸向提高薄膜的穩(wěn)定性和功能最大化方向發(fā)展。本文主要研究了引發(fā)式化學(xué)氣相沉積方法制備功能高分子薄膜,探索了納米尺度調(diào)控對(duì)薄膜結(jié)構(gòu)和功能的優(yōu)化,制備了親水、超親水表面和結(jié)構(gòu)化超疏水、超疏油表面,以及對(duì)不同性質(zhì)表面的應(yīng)用做了初步探索。具體研究?jī)?nèi)容和成果如下:1.親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)作為交聯(lián)劑,通過(guò)控制單體流量比得到了不同交聯(lián)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))。對(duì)于平面和非平面基底分別采用直接接枝和分層原位接枝的方法提高薄膜與基底的結(jié)合強(qiáng)度。薄膜的親水性以及抗生物吸附性隨著交聯(lián)度的減小而增加,平面基底和非平面基底最小水接觸角分別為33±1o和0o。親水改性的聚偏氟乙烯濾膜對(duì)蛋白質(zhì)的吸附最佳效果減少了92%,并且能夠有效減少大腸桿菌的吸附。直接接枝和雙層原位接枝兩種薄膜經(jīng)長(zhǎng)期水洗和超聲處理后都能保持結(jié)構(gòu)和功能的穩(wěn)定性。2.我們?cè)赑(VP-co-EGDA)薄膜生長(zhǎng)過(guò)程中原位接枝PVP,進(jìn)一步提高了薄膜的親水性與生物相容性。XPS測(cè)試結(jié)果表明,接枝PVP后相比于交聯(lián)度最低的P(VP-co-EGDA)表面N元素的含量增加37%,表明內(nèi)酰胺基團(tuán)數(shù)量大大增加。水接觸角測(cè)試結(jié)果中,接枝PVP的表面接觸角進(jìn)一步減小了11o。我們分別采用P(VP-co-EGDA)和P(VP-co-EGDA)基礎(chǔ)上原位復(fù)合接枝PVP的薄膜對(duì)醫(yī)用導(dǎo)管進(jìn)行親水改性,改性后導(dǎo)管水接觸角分別為38o和28o。然后將這兩種薄膜改性的導(dǎo)管植入小鼠皮下進(jìn)行生物相容性測(cè)試,結(jié)果表明改性的導(dǎo)管相比未改性的導(dǎo)管生物相容性都有提高,其中經(jīng)過(guò)原位接枝PVP的導(dǎo)管生物組織相容性效果更佳。3.氣相法單步制備聚合物納米陣列。在全氟癸基丙烯酸酯(PFDA)沉積過(guò)程中引入EGDA促使PPFDA納米陣列結(jié)構(gòu)的形成,通過(guò)調(diào)節(jié)EGDA和PFDA分壓得到了不同密度和形貌的PPFDA納米錐陣列,結(jié)構(gòu)尺寸隨著沉積時(shí)間的增加而增加。這種有序的PPFDA納米錐陣列的形成具有基底普適性,由于全氟側(cè)鏈極低的表面能和納米粗糙度賦予了表面超疏水、超疏油的特性,其中在棉布表面水、甘油、乙二醇、二碘甲烷、菜油接觸角均在170o以上,辛烷接觸角在150o以上;納米陣列修飾的硅片表面接觸角前進(jìn)角為162o,后退角為158o,滑動(dòng)角小于1o。這種氣相構(gòu)筑聚合物納米陣列的研究成果在制備超疏水超疏油表面以及聚合物納米結(jié)構(gòu)化生長(zhǎng)方面均具有突破性的意義。本文通過(guò)以上三個(gè)部分的工作探索了氣相法納米尺度調(diào)控對(duì)薄膜穩(wěn)定性、功能性以及表面結(jié)構(gòu)化的影響和作用,為制備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 鹵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.
【學(xué)位授予單位】：寧波大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TB383.2;TQ317
本文編號(hào)：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 鹵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.
【學(xué)位授予單位】：寧波大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TB383.2;TQ317
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