發(fā)布時間：2018-06-07 14:28

  本文選題：側(cè)鏈 + 液晶聚合物　； 參考：《蘇州大學(xué)》2016年碩士論文

【摘要】：在側(cè)鏈型液晶聚合物中,側(cè)鏈扮演了一個十分重要的角色,它將影響組裝結(jié)構(gòu),并表達出豐富的功能性。因此本論文從側(cè)鏈的分子結(jié)構(gòu)設(shè)計出發(fā),通過系統(tǒng)變化側(cè)鏈的結(jié)構(gòu)來考察側(cè)鏈與主鏈之間的相互作用對聚合物組裝結(jié)構(gòu)的影響。合成了一系列以聚降冰片烯為主鏈,側(cè)鏈包含剛性聯(lián)苯結(jié)構(gòu)和柔性尾鏈(CmBA)的液晶聚合物。具體的研究內(nèi)容如下:(1)合成了一系列介晶單元個數(shù)、位置、烷基尾鏈長度各不相同的降冰片烯類液晶小分子單體NB-4-Cm BA,NB-3,5-CmBA,NB-3,4-CmBA和NB-3,4,5-CmBA(m=12,16),通過氫核磁共振(1H NMR)、碳核磁共振(13C NMR)以及高分辨質(zhì)譜的表征驗證了結(jié)構(gòu)的準(zhǔn)確性,同時通過差示掃描量熱法(DSC)、偏光顯微鏡(POM)對單體的液晶相行為進行研究。結(jié)果表明對于同一個系列,在烷基尾鏈較長時,烷基尾鏈碳原子個數(shù)的增加可以提高清亮點(Ti)的溫度;CmBA個數(shù)、取代位置的變化會較大的影響單體的相結(jié)構(gòu),形成不同的液晶織構(gòu)。(2)采用三代Grubbs催化劑進行開環(huán)易位聚合反應(yīng)(ROMP),得到對應(yīng)的聚降冰片烯類側(cè)鏈型液晶聚合物(PNB-4-CmBA,PNB-3,5-CmBA,PNB-3,4-CmBA和PNB-3,4,5-CmBA,m=12,16)。通過1H NMR、凝膠滲透色譜法(GPC)對分子結(jié)構(gòu)進行了表征,熱重分析(TGA)結(jié)果表明分子熱穩(wěn)定性較好。結(jié)合DSC、POM、小角X射線散射(SAXS)、同步輻射SAXS、二維X射線廣角衍射(WAXD)研究了聚合物的相結(jié)構(gòu)和相轉(zhuǎn)變行為。側(cè)鏈只含一個CmBA的PNB-4-CmBA表現(xiàn)出SmA相;當(dāng)側(cè)鏈含兩個CmBA,且為鄰位取代時,PNB-3,4-CmBA表現(xiàn)出具有帶心長方點陣結(jié)構(gòu)的受挫近晶相(Φr-c);當(dāng)兩個CmBA為間位取代時,聚合物PNB-3,5-CmBA不表現(xiàn)出液晶性;當(dāng)側(cè)鏈含有3個CmBA時,聚合物PNB-3,4,5-CmBA表現(xiàn)出六方柱狀相(Φh)結(jié)構(gòu)。結(jié)果表明隨著側(cè)鏈部分CmBA的數(shù)量增加,聚合物發(fā)生了從SmA到無定型、Φr-c再到Φh相的變化。具有剛?cè)崆抖谓Y(jié)構(gòu)的CmBA之間傾向于彼此平行排列,形成層狀結(jié)構(gòu),而當(dāng)側(cè)鏈部分同時接入兩個以上的CmBA后,相鄰CmBA之間由于空阻的作用存在一定夾角,在一定程度上抑制了平行排列的穩(wěn)定性,導(dǎo)致層狀結(jié)構(gòu)受挫;另一方面,隨著側(cè)鏈部分CmBA數(shù)量的增加,非極性脂肪鏈部分所占的體積百分含量隨之增加,導(dǎo)致相分離界面曲率發(fā)生變化,最終形成了之前所述的相結(jié)構(gòu)演變過程。(3)合成了PNB-6-3,4-CmBA(m=8,12),研究了柔性間隔基、非極性脂肪鏈長度變化對鄰位取代雙液晶基元聚合物的液晶行為的影響,DSC、POM和SAXS研究表明柔性間隔基增加后,這類聚合物仍然可形成Φr-c相,表現(xiàn)出鄰位取代雙液晶基元型側(cè)鏈在聚合物形成這類特殊液晶相態(tài)時起了重要作用。采用原子力顯微鏡(AFM)方法研究了薄膜樣品的相結(jié)構(gòu)形貌。
[Abstract]:Side chain plays a very important role in the side chain liquid crystal polymer, which will affect the assembly structure and express rich functionality. Therefore, from the molecular structure design of the side chain, the influence of the interaction between the side chain and the main chain on the polymer assembly structure is investigated by changing the structure of the side chain. A series of liquid crystalline polymers with rigid biphenyl structure and flexible tail chain (CmBA) were synthesized with polynorbornene as the main chain. The specific research contents are as follows: (1) the number and position of a series of mesocrystalline units have been synthesized. The molecular monomers of norbornene liquid crystal with different alkyl tail chain lengths, NB-4-Cm BANB-3, 5-CmBABA-4-CmBA and NB-3O45-CmBAMN 1216, were characterized by 1H NMR, 13C NMRs and high resolution mass spectrometry (HRMS) to verify the accuracy of the structure. At the same time, the liquid crystal phase behavior of monomers was studied by differential scanning calorimetry (DSC) and polarizing microscope (POM). The results show that for the same series, when the alkyl tail chain is longer, the increase of the number of carbon atoms in the alkyl tail chain can increase the temperature of CmBA, and the change of substitution position will greatly affect the phase structure of the monomer. The third generation Grubbs catalyst was used to carry out ring-opening and translocation polymerization. The corresponding side chain liquid crystal polymers (PNB-4-CmBAPNB-3-CmBAPNB-3-CmBA4-CmBA and PNB-345-CmBAmB) were obtained. The molecular structure was characterized by 1H-NMR-gel permeation chromatography (GPC) and thermogravimetric analysis (TGA) showed that the molecular thermal stability was better. The phase structure and phase transition behavior of the polymer were studied by means of DSC-POM, small-angle X-ray scattering, synchrotron radiation (SAXS) and two-dimensional X-ray wide-angle diffraction (WAXD). When the side chain contains only one CmBA, the PNB-4-CmBA exhibits SmA phase, when the side chain contains two CmBAs and is the adjacent substitution, the PNB-3PNB-34-CmBA exhibits a frustrated near crystalline phase (桅 r-che) with a central rectangular lattice structure, and when two CmBA are intersite substituted, the polymer PNB-35-CmBA does not exhibit liquid crystal properties. When the side chain contains three CmBA, the polymer PNB-3CmBA exhibits a hexagonal columnar phase (桅 h) structure. The results show that with the increase of the number of CmBA in the side chain, the polymer changes from SmA to amorphous, 桅 r-c to 桅 h phase. The CmBA with rigid and flexible block structure tends to be arranged parallel to each other and cambiform structure. However, when the side chain part is connected to more than two CmBA at the same time, there is a certain angle between the adjacent CmBA due to the effect of air resistance. On the other hand, with the increase of the number of CmBA in the side chain, the percentage of the volume of the non-polar fat chain increases. As a result, the curvature of the phase separation interface changed, resulting in the formation of the evolution process of the phase structure. The PNB-6-3 4-CmBAMN 812N was synthesized, and the flexible spacer base was studied. Effect of the length of nonpolar fat chain on the liquid crystal behavior of ortho substituted double liquid crystalline polymer the results of DSC-POM and SAXS show that the 桅 r-c phase can still be formed when the flexible spacer is increased. It is shown that the side chains of ortho substituted double liquid crystal units play an important role in the formation of such special liquid crystal phase states. The phase structure and morphology of thin films were studied by atomic force microscopy (AFM).
【學(xué)位授予單位】：蘇州大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：O753.2;O631

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