共缩聚聚酰胺的设计合成及其自组装与响应特性研究
发布时间：2018-08-04 09:33
【摘要】：嵌段共聚物是当前大分子自组装研究的主体,和嵌段共聚物相比,缩聚物也是一类非常重要的聚合物材料,然而目前基于缩聚物溶液自组装的研究报道还不多。聚酰胺作为一类重要的缩聚物,一般是由二元酸和二元胺缩聚而成。聚酰胺分子中存在强分子间氢键作用,可以赋予聚酰胺组装体基于强氢键的高稳定性和环境响应性;聚酰胺具有一定的结晶性,可以赋予其结晶诱导或驱动的“活性自组装”能力;此外,还可以通过简单的共缩聚在聚酰胺中引入功能性分子。因此,聚酰胺有望成为一类新的大分子自组装基元,但相关研究迄今鲜有报道。基于此,本论文合成了一系列具有不同刺激响应性单元的两亲性共聚酰胺,细致研究了合成聚酰胺在水中的自组装行为,积极探求其自组装规律和应用领域。本论文具体研究内容和结论如下:首先合成了亲水嵌段和疏水嵌段比值约为0.4:1的多嵌段共聚酰胺MBCPA,同时为了结构证明的需要,合成了半芳香聚酰胺PA6SIP和传统的聚酰胺PA66;利用FT-IR,1H NMR,TGA和DSC等测试方法对合成聚酰胺的结构进行了表征,结果表明MBCPA具有预期的化学结构和多嵌段结构;通过直接水合法,制备了该聚酰胺的组装体,DLS,AFM和TEM结果表明MBCPA在水中可以组装成壁厚仅为4.5nm的超薄聚酰胺囊泡;利用耗散粒子动力学(DPD)和TEM揭示了自组装机理,结果表明其组装机理可以概括为“胶束-薄膜-囊泡”,并且囊泡中聚酰胺分子链呈现折叠链,悬挂链和横跨链三种分子折叠模式;通过简单的共混搅拌,将疏水的模型药物分子尼罗红染料包裹进MBCPA囊泡的疏水壁中,荧光光谱(FL)和TEM结果表明MBCPA囊泡具有超声响应性,在外界超声作用下,仅需要14 min,就可以释放出50%的模型药物尼罗红;Micro-dsc和FT-IR的结果证明MBCPA囊泡超声响应性的本质是超声会破坏囊泡中聚酰胺分子间的氢键。以pH响应性基团1,4-双(3-氨基丙基)哌嗪和α,ω-二羧基聚乙二醇为原料,合成了pH响应性聚酰胺PAPIP.26;利用FT-IR,1H NMR,和GPC等测试手段对合成产物的化学结构进行了表征,结果表明合成产物是具有预期结构的聚酰胺;通过直接水合法,制备了PAPIP.26组装体。AFM和SEM的结果表明组装液浓度为0.6mg/mL时,合成的聚酰胺可以组装成轴向长度大于20μm,厚度超过500nm的巨型椭圆片;浓度增加到1mg/mL时,巨型椭圆片会进一步自组装成多角的超级结构;利用AFM和SEM跟踪拍摄不同浓度(c=0.01mg/mL,0.05mg/mL和0.6mg/mL)下组装体的形貌,结果表明巨型椭圆片是由棱台状小片经过多级层层自组装过程形成的,并将整个自组装过程定义为装置艺术多级自组装;WXRD和SAXS结果表明,PAPIP.26在水溶液中会折叠成一个厚度为12.32nm的有序片层状结构。在这个有序的片层状结构中,包括二条伸直的PEG units和三条倾斜的PIP units,并且在这个有序的层状结构表面,PAPIP.26分子链会通过PEG segment的弯曲折叠,形成一个连续的,完整的链折叠结构;最后,通过调节溶液的pH值,当pH值为0.5,1.0,1.5和2.0时,PAPIP.26在水溶液中可以分别组装成麦穗状超级结构,脑回状超级结构,青蛙卵状超级结构和矩形片组装体。以含有温度响应性PPG链段的聚醚胺和己二酸为原料,合成了温度响应性聚酰胺APA;FT-IR和GPC的结果表明合成产物是具有酰胺结构的聚合物;Micro-dsc和变温紫外的结果表明,合成的APA具有33oC的最低临界互溶温度;TEM和AFM的结果表明组装体溶液浓度为1mg/mL时,APA在常温下可以组装成一维的长纤维,而当温度升为60oC,这些一维的长纤维会转变为平均螺距为35nm的螺旋纤维。在APA的合成基础上,以温度响应性的α,ω-二羧基聚乙二醇和光响应性的对二氨基偶氮苯为原料,合成了温度和光双重响应的聚酰胺PAAzo.26;FT-IR,1H NMR,和GPC的结果表明合成产物具有预期分子结构;TEM的结果表明,在升温过程中,PAAzo.26组装体形貌经历了“不规则胶束-球形胶束”的形貌转变;而在紫外光照射下,PAAzo.26的组装体经历了“多分子胶束-空化的胶束-具空腔的核壳结构-不完全囊泡-胶束囊泡”的形貌转变过程;紫外可见光谱的结果表明PAAzo.26光响应性的本质是紫外光会使聚酰胺中偶氮苯基团发生顺反异构化;FL的结果表明PAAzo.26组装体具有典型的聚集诱导发光行为,并且体系具有超强的抗光漂白性;此外,本体系还具有独特的上转换特性,可以用波长较长而能量较低的近红外光源激发,得到波长较短而能量较高的绿色荧光。
[Abstract]:Block copolymers are the main body of current large molecular self-assembly studies. Compared with block copolymers, polypolymers are also a very important class of polymer materials. However, there are still few reports on self assembly based on polycondensation. Polyamides are a class of important polycondensation, in the same way polyamides are made from diacids and two amines. Polyamides are made. The presence of hydrogen bonds between strong molecules can endow the polyamide assembly with high stability and environmental responsiveness based on strong hydrogen bonds. Polyamide has a certain crystalline property, which can give its crystallization induced or driven "active self assembly" ability. In addition, the polyamide can also be introduced to the polyamide by simple co condensation to introduce functional molecules. Therefore, polyamide is expected to become a new class of macromolecule self-assembly primitives, but the related research has not been reported so far. Based on this, a series of two Pro copolymerized amides with different stimulus response units have been synthesized in this paper. The self-assembly behavior of synthetic polyamide in water is carefully studied, and its self-assembly and application fields are actively explored. The contents and conclusions of this paper are as follows: firstly, the polyamide MBCPA of 0.4:1 is synthesized by the hydrophilic block and the hydrophobic block ratio is about 0.4:1, and the semi aromatic polyamide and the traditional polyamide PA66 are synthesized for the need of the structural proof, and the structure of the synthetic polyamide is used by the methods of FT-IR, 1H NMR, TGA and DSC. The results showed that MBCPA had the expected chemical structure and multi block structure. By direct water method, the assembly of the polyamide was prepared. The results of DLS, AFM and TEM showed that MBCPA could be assembled into a super thin polyamide vesicle with a thickness of only 4.5nm in water, and the mechanism of self-assembly was revealed by the dissipative particle dynamics (DPD) and TEM. It is shown that the assembly mechanism can be summarized as "micelle film - vesicles", and the polyamide molecular chain in the vesicles is folded chain, suspended chain and cross chain three kinds of molecular folding modes. Through simple mixing, the hydrophobic model drug molecule Nile red dye is wrapped in the hydrophobic wall of MBCPA vesicles, fluorescence spectrum (FL) and TEM result table. The clear MBCPA vesicles have ultrasonic responsiveness. Under the external ultrasonic action, only 14 min is needed to release 50% of the model drug Nile red. The results of Micro-dsc and FT-IR show that the essence of the ultrasonic responsiveness of the MBCPA vesicles is that ultrasound will destroy the hydrogen bonds between the polyamide molecules in the vesicles. The pH responsive group 1,4- double (3- amino propyl) piperazine and alpha. PH responsive polyamide PAPIP.26 was synthesized from Omega two carboxyl polyethylene glycol, and the chemical structure of the synthesized product was characterized by means of FT-IR, 1H NMR, and GPC. The results showed that the synthesized product was a polyamide with the expected structure. The result of the preparation of the.AFM and SEM of the PAPIP.26 assembly by direct water method showed the assembly solution. When the concentration is 0.6mg/mL, the synthesized polyamide can be assembled into a giant ellipse with an axial length greater than 20 u m and a thickness exceeding 500nm. When the concentration increases to 1mg/mL, the giant ellipsoid will be further self assembled into a multi angle superstructure, and the morphology of the assemblies under different concentrations (c= 0.01mg/mL, 0.05mg/mL and 0.6mg/mL) is followed by AFM and SEM. The results show that the giant ellipsoid is formed by a multilevel self-assembly process of prismatic flake, and the whole self-assembly process is defined as the multilevel self-assembly of the device art. The results of WXRD and SAXS show that PAPIP.26 will fold into an ordered lamellar structure with a thickness of 12.32nm in the aqueous solution. Including two straight PEG units and three tilted PIP units, and on this ordered layered structure surface, the PAPIP.26 molecular chain will fold through the bending of PEG segment to form a continuous, complete chain folding structure; finally, by adjusting the pH value of the solution, when the pH value is 0.5,1.0,1.5 and 2, PAPIP.26 in aqueous solution can be separated. A spike like superstructure, a gyrus superstructure, a frog oval superstructure and a rectangular piece assembly were assembled. The temperature responsive polyether amines and adipic acid were used as raw materials to synthesize the temperature responsive polyamide APA; the results of FT-IR and GPC showed that the synthesized product was a polymer with amidic structure; Micro-dsc and temperature variant UV The results show that the synthesized APA has the lowest critical intermiscible temperature of 33oC, and the results of TEM and AFM show that when the concentration of the assembly solution is 1mg/mL, APA can be assembled into a one-dimensional long fiber at normal temperature, and when the temperature rises to 60oC, these one-dimensional long fibers will turn into the spiral fibers with an average pitch of 35nM. On the basis of APA, the temperature will be temperature. The degree responsive alpha, Omega two carboxyl polyethylene glycol and photoresponse of two amino azobenzene as raw material, synthesized the double response of temperature and light polyamide PAAzo.26; FT-IR, 1H NMR, and GPC showed that the synthesized product had the expected molecular structure; the result of TEM showed that the shape appearance of PAAzo.26 assembly experienced "irregular" during the process of rising temperature. The morphologies of the micellar spherical micelle, while under ultraviolet light, the PAAzo.26's assembly experienced the transformation process of "multi molecule micelle - cavitation micelle - the nucleus shell structure of the cavity - the incomplete vesicles - micellar vesicles". The UV visible spectrum shows that the essence of the PAAzo.26 light response is that ultraviolet light will make polyamides. The azobenzene group has CIS and trans isomerization. The results of FL show that the PAAzo.26 assembly has a typical aggregation induced luminescence behavior, and the system has super photobleaching resistance. In addition, the system has unique upconversion properties, which can be excited by a near infrared light source with a longer wavelength and lower energy, which has shorter wavelengths and higher energy. Green fluorescence.
【学位授予单位】：哈尔滨工业大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O633.22
[Abstract]:Block copolymers are the main body of current large molecular self-assembly studies. Compared with block copolymers, polypolymers are also a very important class of polymer materials. However, there are still few reports on self assembly based on polycondensation. Polyamides are a class of important polycondensation, in the same way polyamides are made from diacids and two amines. Polyamides are made. The presence of hydrogen bonds between strong molecules can endow the polyamide assembly with high stability and environmental responsiveness based on strong hydrogen bonds. Polyamide has a certain crystalline property, which can give its crystallization induced or driven "active self assembly" ability. In addition, the polyamide can also be introduced to the polyamide by simple co condensation to introduce functional molecules. Therefore, polyamide is expected to become a new class of macromolecule self-assembly primitives, but the related research has not been reported so far. Based on this, a series of two Pro copolymerized amides with different stimulus response units have been synthesized in this paper. The self-assembly behavior of synthetic polyamide in water is carefully studied, and its self-assembly and application fields are actively explored. The contents and conclusions of this paper are as follows: firstly, the polyamide MBCPA of 0.4:1 is synthesized by the hydrophilic block and the hydrophobic block ratio is about 0.4:1, and the semi aromatic polyamide and the traditional polyamide PA66 are synthesized for the need of the structural proof, and the structure of the synthetic polyamide is used by the methods of FT-IR, 1H NMR, TGA and DSC. The results showed that MBCPA had the expected chemical structure and multi block structure. By direct water method, the assembly of the polyamide was prepared. The results of DLS, AFM and TEM showed that MBCPA could be assembled into a super thin polyamide vesicle with a thickness of only 4.5nm in water, and the mechanism of self-assembly was revealed by the dissipative particle dynamics (DPD) and TEM. It is shown that the assembly mechanism can be summarized as "micelle film - vesicles", and the polyamide molecular chain in the vesicles is folded chain, suspended chain and cross chain three kinds of molecular folding modes. Through simple mixing, the hydrophobic model drug molecule Nile red dye is wrapped in the hydrophobic wall of MBCPA vesicles, fluorescence spectrum (FL) and TEM result table. The clear MBCPA vesicles have ultrasonic responsiveness. Under the external ultrasonic action, only 14 min is needed to release 50% of the model drug Nile red. The results of Micro-dsc and FT-IR show that the essence of the ultrasonic responsiveness of the MBCPA vesicles is that ultrasound will destroy the hydrogen bonds between the polyamide molecules in the vesicles. The pH responsive group 1,4- double (3- amino propyl) piperazine and alpha. PH responsive polyamide PAPIP.26 was synthesized from Omega two carboxyl polyethylene glycol, and the chemical structure of the synthesized product was characterized by means of FT-IR, 1H NMR, and GPC. The results showed that the synthesized product was a polyamide with the expected structure. The result of the preparation of the.AFM and SEM of the PAPIP.26 assembly by direct water method showed the assembly solution. When the concentration is 0.6mg/mL, the synthesized polyamide can be assembled into a giant ellipse with an axial length greater than 20 u m and a thickness exceeding 500nm. When the concentration increases to 1mg/mL, the giant ellipsoid will be further self assembled into a multi angle superstructure, and the morphology of the assemblies under different concentrations (c= 0.01mg/mL, 0.05mg/mL and 0.6mg/mL) is followed by AFM and SEM. The results show that the giant ellipsoid is formed by a multilevel self-assembly process of prismatic flake, and the whole self-assembly process is defined as the multilevel self-assembly of the device art. The results of WXRD and SAXS show that PAPIP.26 will fold into an ordered lamellar structure with a thickness of 12.32nm in the aqueous solution. Including two straight PEG units and three tilted PIP units, and on this ordered layered structure surface, the PAPIP.26 molecular chain will fold through the bending of PEG segment to form a continuous, complete chain folding structure; finally, by adjusting the pH value of the solution, when the pH value is 0.5,1.0,1.5 and 2, PAPIP.26 in aqueous solution can be separated. A spike like superstructure, a gyrus superstructure, a frog oval superstructure and a rectangular piece assembly were assembled. The temperature responsive polyether amines and adipic acid were used as raw materials to synthesize the temperature responsive polyamide APA; the results of FT-IR and GPC showed that the synthesized product was a polymer with amidic structure; Micro-dsc and temperature variant UV The results show that the synthesized APA has the lowest critical intermiscible temperature of 33oC, and the results of TEM and AFM show that when the concentration of the assembly solution is 1mg/mL, APA can be assembled into a one-dimensional long fiber at normal temperature, and when the temperature rises to 60oC, these one-dimensional long fibers will turn into the spiral fibers with an average pitch of 35nM. On the basis of APA, the temperature will be temperature. The degree responsive alpha, Omega two carboxyl polyethylene glycol and photoresponse of two amino azobenzene as raw material, synthesized the double response of temperature and light polyamide PAAzo.26; FT-IR, 1H NMR, and GPC showed that the synthesized product had the expected molecular structure; the result of TEM showed that the shape appearance of PAAzo.26 assembly experienced "irregular" during the process of rising temperature. The morphologies of the micellar spherical micelle, while under ultraviolet light, the PAAzo.26's assembly experienced the transformation process of "multi molecule micelle - cavitation micelle - the nucleus shell structure of the cavity - the incomplete vesicles - micellar vesicles". The UV visible spectrum shows that the essence of the PAAzo.26 light response is that ultraviolet light will make polyamides. The azobenzene group has CIS and trans isomerization. The results of FL show that the PAAzo.26 assembly has a typical aggregation induced luminescence behavior, and the system has super photobleaching resistance. In addition, the system has unique upconversion properties, which can be excited by a near infrared light source with a longer wavelength and lower energy, which has shorter wavelengths and higher energy. Green fluorescence.
【学位授予单位】：哈尔滨工业大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O633.22
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