發(fā)布時(shí)間：2018-05-04 12:29

  本文選題：環(huán)狀聚合物 + 點(diǎn)擊化學(xué)�。� 參考：《安徽大學(xué)》2017年碩士論文

【摘要】：目前,具有拓?fù)浣Y(jié)構(gòu)的環(huán)狀高分子是高分子研究的一個(gè)熱點(diǎn)。與線形聚合物相比,環(huán)狀高分子具有比較特殊的性質(zhì),如熱穩(wěn)定性、化學(xué)穩(wěn)定性的提高,流體動(dòng)力學(xué)體積的減小等等。一般來說,線形聚合物在作為生物醫(yī)用組織工程材料時(shí)表面比較光滑,生物相容性較差,會(huì)造成嚴(yán)重的組織反應(yīng),而拓?fù)浣Y(jié)構(gòu)聚合物材料的表面比較粗糙,像海綿狀、纖維狀等等,生物相容性較好,因此環(huán)狀拓?fù)浣Y(jié)構(gòu)聚合物材料在生物醫(yī)用領(lǐng)域有很大的應(yīng)用前景。但環(huán)狀聚合物合成過程復(fù)雜、端基官能團(tuán)反應(yīng)活性低,使環(huán)狀拓?fù)浣Y(jié)構(gòu)聚合物的合成與結(jié)構(gòu)表征工作復(fù)雜且極具挑戰(zhàn)性。而活性自由基聚合的鏈末端高活性和"點(diǎn)擊"化學(xué)的高選擇性相結(jié)合可以大大解決這個(gè)問題,其中以原子轉(zhuǎn)移自由基活性聚合(ATRP)與一價(jià)銅鹽催化的炔基/疊氮偶極環(huán)加成反應(yīng)(CuAAC)相結(jié)合的方法最為典型,使其越來越備受關(guān)注。本文的研究?jī)?nèi)容主要包含:第一章簡(jiǎn)要地介紹了環(huán)狀聚合物的結(jié)構(gòu)、性質(zhì)和合成方法,重點(diǎn)闡述了幾種點(diǎn)擊化學(xué)與活性聚合聯(lián)用制備環(huán)狀聚合物的方法,其中以"點(diǎn)擊"化學(xué)中的一價(jià)銅鹽催化的炔基/疊氮偶極環(huán)加成反應(yīng)(CuAAC)與原子轉(zhuǎn)移自由基活性聚合(ATRP)聯(lián)用的方法適用范圍更廣,產(chǎn)率較高,實(shí)驗(yàn)操作最簡(jiǎn)單。進(jìn)一步闡明了兩親性環(huán)狀聚合物膠束的制備方法以及近幾年來兩親性環(huán)狀聚合物膠束的國(guó)內(nèi)外研究現(xiàn)狀。第二章結(jié)合原子轉(zhuǎn)移自由基活性聚合(ATRP)和"點(diǎn)擊"化學(xué)中銅鹽催化的炔基/疊氮偶極環(huán)加成(CuAAC)反應(yīng),可控合成兩親性環(huán)狀聚(ε-己內(nèi)酯-b-乙烯基吡咯烷酮)嵌段共聚物(Cyclic-PCL-b-PVP),通過傅立葉變換紅外光譜(FT-IR)、核磁共振氫譜(1H-NMR)和凝膠滲透色譜(GPC)分別表征聚合物的結(jié)構(gòu)、分子量及分子量分布,表明兩親性Cyclic-PCL-b-PVP的成功合成。利用熱重分析(TGA)、接觸角和X射線衍射(XRD)的測(cè)試,分別研究了兩親性嵌段共聚物的熱學(xué)性能、親水性能和結(jié)晶性能,結(jié)果表明,相比于線形聚(ε-己內(nèi)酯-b-乙烯基吡咯烷酮)嵌段共聚物(Linear-PCL-b-PVP),相應(yīng)的環(huán)狀嵌段共聚物的熱穩(wěn)定性明顯提高,親水性和結(jié)晶性能亦有所變化。第三章主要利用第二章合成的產(chǎn)物環(huán)狀Cyclic-PCL-b-PVP嵌段共聚物用透析法進(jìn)行自組裝成為膠束聚集體,并將其作為藥物載體對(duì)吲哚美辛藥物進(jìn)行負(fù)載,用芘熒光探針、馬爾文納米激光粒徑儀和透射電子顯微鏡(TEIM)分別測(cè)定了線狀、環(huán)狀PCL-b-PVP嵌段共聚物的臨界膠束濃度(CMC)、膠束的粒徑和形貌,結(jié)果表明線狀、環(huán)狀PCL-b-PVP嵌段共聚物的CMC均較小,得到的膠束穩(wěn)定性良好;相比于線形聚合物膠束的粒徑,由于成環(huán)后無分子鏈末端,聚合物鏈排列較為規(guī)整和緊密,使環(huán)狀Cyclic-PCL-b-PVP嵌段共聚物膠束的粒徑較小。從TEM圖中可以明顯看出PCL-b-PVP嵌段共聚物膠束基本呈現(xiàn)球形,載藥后的嵌段共聚物膠束粒徑相對(duì)較大,這是由于成功包載藥物的緣故。第四章采用ATRP和"點(diǎn)擊"化學(xué)中的CuAAC相結(jié)合的方法,可控合成了環(huán)狀聚(ε-己內(nèi)酯-b-(N-異丙基丙烯酰胺))(Cyclic-PCL-b-PNIPAM)溫敏性嵌段共聚物。采用FT-IR、1H-NMR和GPC方法表征了其共聚產(chǎn)物的結(jié)構(gòu)、分子量及分子量分布。用TGA、DSC、接觸角和XRD的方法,研究了環(huán)狀嵌段共聚物的熱穩(wěn)定性、溫敏性、親水性和結(jié)晶性能的變化。相比于PCL-b-PNIPAM線形嵌段共聚物,由于聚合物成環(huán)后無分子鏈末端,其鏈的解聚較為困難,則相應(yīng)的熱穩(wěn)定性提高;PNIPAM溫敏性鏈段的相轉(zhuǎn)變溫度表現(xiàn)為37.5℃;親水性和結(jié)晶性亦有所變化。第五章主要利用第四章成功合成的產(chǎn)物溫敏性環(huán)狀Cyclic-PCL-b-PNIPAM嵌段共聚物用透析法進(jìn)行自組裝形成膠束聚集體,并將其作為藥物載體對(duì)吲哚美辛藥物進(jìn)行負(fù)載,用芘熒光探針、馬爾文納米激光粒徑儀和TEM的方法分別測(cè)定了線狀、環(huán)狀PCL-b-PNIPAM嵌段共聚物的CMC、膠束的粒徑和形貌,研究表明:線狀、環(huán)狀PCL-b-PNIPAM嵌段共聚物的CMC均較小,得到的膠束穩(wěn)定性良好;相比于線形聚合物前體膠束的粒徑,由于成環(huán)后無分子鏈末端,聚合物鏈排列較為規(guī)整和緊密,使Cyclic-PCL-b-PNIPAM共聚物膠束的粒徑較小;TEM結(jié)果表明PCL-b-PN][PAM嵌段共聚物膠束基本呈現(xiàn)球形,載藥后的嵌段共聚物膠束由于成功包載了吲哚美辛藥物,其粒徑相對(duì)較大。
[Abstract]:At present, circular polymers with topological structures are a hot topic in the study of polymer. Compared with linear polymers, circular polymers have special properties, such as thermal stability, chemical stability, and the decrease of the volume of fluid dynamics. Generally speaking, linear polymers are on the surface of biomedical engineering materials. The smooth and poor biocompatibility will cause serious tissue reaction, and the surface of the topological polymer material is rough, such as spongy, fibrous and so on, and the biocompatibility is good. Therefore, the ring topology polymer material has a great application prospect in the biomedical field, but the ring polymer synthesis process is complex and the end group is complex. The low reactive activity of functional groups makes the synthesis and structural characterization of a cyclic topological polymer complex and challenging. The combination of the high activity of the terminal chain at the end of the active radical polymerization and the high selectivity of "click" chemistry can greatly solve this problem, in which the atom transfer radical active polymerization (ATRP) is catalyzed by the monovalent copper salt. The method of combining alkynyl / AZO dipolar cycloaddition reaction (CuAAC) is the most typical one, making it more and more concerned. The main contents of this paper include: in the first chapter, the structure, properties and synthesis methods of cyclic polymers are briefly introduced, and several methods for the preparation of cyclic polymers by clicking chemistry and active polymerization are emphasized. The method of combination of alkynyl / AZO dipole ring addition reaction (CuAAC) with atom transfer radical active polymerization (ATRP) catalyzed by one valence copper salt in "click" chemistry is more widely used, the yield is higher, and the experimental operation is the simplest. The preparation method of two amphiphilic ring polymer micelles and the amphiphilic ring polymerization in recent years are further clarified. The second chapter controlled the synthesis of two amphiphilic cyclic poly (caprolactone -b- vinylpyrrolidone) block copolymers (Cyclic-PCL-b-PVP) by combining atomic transfer free radical active polymerization (ATRP) and "clicking" chemical copper salts catalyzed alkynyl / AZO dipole cycloaddition (CuAAC) reaction, and the infrared light was transformed by Fu Liye transformation. Spectrum (FT-IR), nuclear magnetic resonance hydrogen spectrum (1H-NMR) and gel permeation chromatography (GPC) were used to characterize the structure, molecular weight and molecular weight distribution of the polymer respectively, indicating the successful synthesis of two Pro Cyclic-PCL-b-PVP. The thermal properties and hydrophilicity of the two amphiphilic block copolymers were investigated by thermogravimetric analysis (TGA), contact angle and X ray diffraction (XRD). The results show that the thermal stability of the corresponding ring block copolymer is obviously improved and the hydrophilic and crystalline properties are also changed compared to the linear poly (epsilon caprolactone -b- vinylpyrrolidone) block copolymer (Linear-PCL-b-PVP). The third chapter mainly uses the product ring Cyclic-PCL-b-PVP block copolymerization in second chapters. The products were self assembled into micellar aggregates and loaded with indomethacin as drug carriers. A pyrene fluorescent probe, Malvin nano laser particle size analyzer and transmission electron microscope (TEIM) were used to determine the critical micelle concentration (CMC) of a linear, circular PCL-b-PVP block copolymer, the particle size and morphology of the micelle, and the junction of the micelle. The CMC of the ring PCL-b-PVP block copolymer is smaller and the stability of the micelle is good. Compared to the particle size of the linear polymer micelle, the polymer chain is more regular and compact because of the ring free chain end after the ring formation. The particle size of the circular Cyclic-PCL-b-PVP block copolymer micelle is smaller. It can be clearly seen from the TEM diagram. The PCL-b-PVP block copolymer micelles are basically spherical, and the size of the block copolymer micelles after drug loading is relatively large, which is due to the successful loading of the drug. The fourth chapter uses the method of combining the ATRP and the CuAAC in "click" chemistry to synthesize the cyclic poly (epsilon hexyl -b- (N- isopropyl acrylamide)) (Cyclic-PCL-b-PNIPAM) temperature The structure, molecular weight and molecular weight distribution of the copolymers were characterized by FT-IR, 1H-NMR and GPC methods. The thermal stability, temperature sensitivity, hydrophilic and crystalline properties of the ring block copolymers were studied by means of TGA, DSC, contact angle and XRD. Compared to the linear block copolymers of PCL-b-PNIPAM, the polymers were compared with those of the polymer. The depolymerization of the chain is more difficult and the thermal stability of the chain is more difficult. The phase transition temperature of the PNIPAM Wen Min sex segment is 37.5, and the hydrophilicity and crystallinity are also changed. The fifth chapter mainly uses the dialysis method for the thermo sensitive cyclic Cyclic-PCL-b-PNIPAM block copolymer of the products synthesized in the fourth chapters. The micellar aggregates were formed by self assembly and used as drug carriers to load indomethacin. The CMC of linear, ring PCL-b-PNIPAM block copolymers and the size and morphology of the micelles were measured with pyrene fluorescence probe, Malvin nano laser particle size meter and TEM, respectively. The study showed that the linear, circular PCL-b-PNIPAM block copolymer was linear. Compared to the particle size of the linear polymer precursor micelles, the size of the CMC micelles is relatively small and the particle size of the Cyclic-PCL-b-PNIPAM copolymer micelles is relatively small compared to the particle size of the linear polymer precursor micelles. The TEM results show that the PCL-b-PN][PAM block copolymer micelles are basically spherical and after the drug loading. Micelles of block copolymers were successfully coated with indomethacin, and their diameters were relatively large.

【學(xué)位授予單位】：安徽大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O631;TQ460.1

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