【摘要】：疏水締合水凝膠是一種物理交聯(lián)型凝膠,其三維網(wǎng)絡的交聯(lián)點由疏水締合微區(qū)構成。這種疏水基團間的相互作用具有動態(tài)可逆性,故疏水締合水凝膠具有一些傳統(tǒng)化學凝膠所不具備的特殊性能,例如高機械強度、自愈合及二次加工的特性。因此,其在近年來逐漸成為了科研工作者們關注的熱點,并且在油田開采、污水凈化、涂料和生物醫(yī)學等生產生活的各個方面發(fā)揮了重要的作用。當人們都將目光著眼于疏水締合水凝膠作為材料的應用前景上時,凝膠的基礎理論研究卻進展緩慢。一些新型水凝膠的性能與行為缺乏系統(tǒng)的理論支持,造成了性能預判與按需構筑的障礙。比如,同一種凝膠在不同環(huán)境下的性能和行為,與環(huán)境因子對網(wǎng)絡結構的影響息息相關。本文正是以此為出發(fā)點,將問題集中于微環(huán)境對疏水締合水凝膠機械性能與溶脹行為的影響,探究影響因素與機制,并對凝膠內部網(wǎng)絡結構及其性能與行為進行更為深入的研究與探討。因此,本文選用丙烯酰胺(AM)為親水主單體,實驗室自主合成的辛基酚聚氧乙烯(10)醚丙烯酸酯(OP10-AC)為疏水單體,在表面活性劑十二烷基硫酸鈉(SDS)和引發(fā)劑過硫酸鉀(KPS)的作用下,采用膠束共聚合的方法制備所需疏水締合水凝膠,并對其微環(huán)境實施改變,從而進行系統(tǒng)的探究。首先,選取了五組含不同SDS組分的凝膠配比,并將無機鹽NaCl作為改變凝膠微環(huán)境的因素加入到合成體系內,制備出了含有NaCl的疏水締合水凝膠,分別對其機械性能以及溶脹行為進行了研究。通過單向拉伸實驗,得到了凝膠的斷裂強度和模量等宏觀機械性能的參數(shù)。實驗結果顯示,盡管五組凝膠中SDS的含量不同,但其斷裂強度隨NaCl和SDS摩爾比的增加,呈現(xiàn)相同的趨勢,均為“上升-下降-上升-下降”的“M”型走勢。此外,利用Mooney-Rivlin理論計算了凝膠的微觀網(wǎng)絡參數(shù),對凝膠的內部網(wǎng)絡結構進行了剖析,結果表明,NaCl的加入造成凝膠網(wǎng)絡中有效交聯(lián)密度下降,且NaCl加入量越多交聯(lián)密度下降幅度越大。在對凝膠溶脹行為的測定實驗中,可以發(fā)現(xiàn),凝膠的溶脹程度、水中壽命與網(wǎng)絡結構密切相關。結合第二章的實驗結果,可知:有效交聯(lián)密度與溶脹速度和溶脹比呈現(xiàn)反比關系。除此之外,當溶脹介質中含有NaCl時,凝膠的溶脹行為主要受兩方面的影響:一是鹽析作用,其能夠加強疏水締合的強度;二是滲透壓的作用,阻礙凝膠對水分的吸收。在兩種作用的綜合影響下,凝膠在NaCl溶液中溶脹時會具有較低的溶脹比和較長的壽命。其次,除了無機鹽NaCl的影響之外,還探究了環(huán)境因子表面活性劑SDS對凝膠溶脹行為的影響。利用含有SDS的溶液對凝膠進行溶脹測試,是對其微環(huán)境中SDS情況進行改變的方式,并同時能夠得到相應的溶脹行為。結果表明,一方面,SDS作為凝膠合成過程中表面活性劑,其對凝膠疏水締合交聯(lián)點的解締合具有促進作用,加速凝膠的溶脹。另一方面作為一種磺酸鹽,滲透壓會對凝膠的溶脹產生影響,溶脹度會隨著SDS濃度的升高而減小。綜上所述,本篇論文通過改變凝膠中小分子無機鹽NaCl和大分子表面活性劑SDS兩種微環(huán)境因子,對疏水締合水凝膠的機械性能以及溶脹行為進行了相關研究,并對其影響機制、交聯(lián)情況以及內部構筑展開了詳細探討。凝膠在宏觀條件中的種種性能和行為皆歸因于其微環(huán)境下網(wǎng)絡結構的變化。對辛基酚聚氧乙烯醚疏水締合凝膠在微環(huán)境下的機械性能和溶脹行為建立了理論基礎,為準確預判與按需構筑提供了方法,為拓展應用和開辟前景奠定了基石。
[Abstract]:Hydrophobically linked hydrogel is a physical crosslinked gel. The crosslinking point of its three-dimensional network is composed of hydrophobically associating microregions. The interaction between these hydrophobic groups is dynamic and reversible, so hydrophobic hydrogels have special properties that some traditional chemical gels do not possess, such as high mechanical strength, self healing and two processing. Therefore, in recent years, it has become a hot spot of concern for researchers, and plays an important role in all aspects of production and life of oil field mining, sewage purification, coating and biomedicine. When people focus on the application prospect of hydrophobic gel as material, basic theoretical study of gel is studied. However, the performance and behavior of some new hydrogels lack systematic theoretical support, resulting in the barrier of performance prediction and demand. For example, the performance and behavior of the same gel in different environments is closely related to the impact of environmental factors on the network structure. This is the starting point for this paper to focus the problem on the micro environment. The effects of the mechanical properties and swelling behavior of hydrophobically combined hydrogel were investigated, and the influence factors and mechanisms were explored, and the internal network structure and performance and behavior of the gel were further studied and discussed. Therefore, the AM was used as the hydrophilic main monomer and the main synthesis of octyl phenol polyoxyethylene (10) ether acrylate (OP1) in the laboratory. 0-AC) for the hydrophobic monomer, under the action of the surface active agent twelve alkyl sulfate (SDS) and the initiator potassium persulfate (KPS), the hydrophobic combined hydrogel was prepared by the micellar copolymerization, and the microenvironment was changed to make a systematic inquiry. First, five groups of gel ratios containing different SDS components were selected and the inorganic compounds were selected. As a factor to change the microenvironment of the gel, salt NaCl was added into the synthetic system, and the hydrophobic hydrogel containing NaCl was prepared. The mechanical properties and swelling behavior of the gel were studied. The parameters of the macroscopic mechanical properties, such as the fracture strength and modulus of the gel, were obtained by the unidirectional tensile test. The experimental results showed that five groups were in spite of the experimental results. The content of SDS in the gel is different, but the breaking strength of the gel increases with the increase of NaCl and SDS molar ratio, which is the "M" trend of "rise drop - rise - drop". Furthermore, the micro network parameters of the gel are calculated by Mooney-Rivlin theory, and the internal network structure of the gel is analyzed. The results show that NaCl is added. The effective crosslinking density decreased in the gel network, and the more the NaCl added, the greater the cross-linking density decreased. In the test of the swelling behavior of the gel, it is found that the swelling degree of the gel and the life of the water are closely related to the network structure. The effective crosslinking density and swelling speed and dissolution can be found in the second chapters. The swelling ratio is inversely proportional. In addition, when the swelling medium contains NaCl, the swelling behavior of the gel is mainly affected by two aspects: one is the salting out effect, which can strengthen the strength of the hydrophobicity Association; the two is the osmotic pressure, which hinders the absorption of the water. Under the comprehensive effect of two kinds of use, the gel will be swelling in the NaCl solution. It has a lower swelling ratio and longer life. Secondly, in addition to the effect of the inorganic salt NaCl, the effect of the environmental factor surfactant SDS on the swelling behavior of the gel is also explored. The swelling test of the gel with a solution containing SDS is the way to change the SDS condition in the microenvironment, and the corresponding swelling can be obtained at the same time. The results show that, on the one hand, as a surface active agent in the gel synthesis process, SDS promotes the deactivation of the gel hydrophobic association crosslinking point and accelerates the swelling of the gel. On the other hand, as a sulfonate, osmotic pressure will affect the swelling of the gel, and the dilatancy will decrease with the increase of the concentration of SDS. In this paper, the mechanical properties and swelling behavior of hydrophobic connective hydrogel were studied by changing the two microenvironmental factors of NaCl and SDS, and the mechanism, crosslinking and internal construction of the gel were discussed in detail. The properties of the gel in the macro conditions were discussed. The mechanical properties and swelling behavior of octyl polyoxyethylene ether hydrophobically associating gel in microenvironment were established, which provided a method for accurate prediction and construction, and laid the foundation for expanding the application and opening the foreground.
【學位授予單位】：吉林大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O648.17

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