非共價鍵改性可逆共價交聯(lián)網(wǎng)絡的制備及性質研究
發(fā)布時間：2018-08-26 17:12
【摘要】：基于可逆交聯(lián)反應的本征型自修復材料因其能夠自發(fā)的從分子水平上對材料進行修復,延長材料的使用壽命、拓寬材料的應用范圍、降低材料的使用成本而成為研究熱點。共價鍵相對于非共價鍵而言具有更高的鍵能,因此,共價交聯(lián)聚合物相對于非共價交聯(lián)體系來說具有更好的力學強度,更適合于結構材料的使用。將可逆交聯(lián)反應引入共價交聯(lián)聚合物可得到一類新型的具有自修復功能的交聯(lián)聚合物。但是由于可逆共價鍵與傳統(tǒng)共價鍵相比較小的鍵能,使得可逆交聯(lián)聚合物通常達不到理想的強度。因此,在提高可逆交聯(lián)聚合物強度的同時不影響其自修復效果是目前尚待解決的一個難題。為提高材料的力學性能,生物體常采用的一種方法為在材料中引入非共價鍵作為犧牲鍵,當受外力作用時,非共價鍵首先發(fā)生斷裂消耗部分能量而保證了材料不受破壞。采用仿生的方法,在可逆共價交聯(lián)聚合物中引入非共價鍵有望進一步提高其力學性能,而非共價鍵本身具有的可逆特性不會影響其自修復效果。本論文以二硫鍵及Zn~(2+)-咪唑配位鍵為基礎,設計合成了共價與非共價雙交聯(lián)聚合物網(wǎng)絡,以及共價交聯(lián)及非共價交聯(lián)互穿網(wǎng)絡兩種交聯(lián)聚合物體系來研究非共價鍵的引入以及非共價交聯(lián)在可逆共價交聯(lián)網(wǎng)絡中的引入方式對可逆共價交聯(lián)聚合物的影響,采用核磁共振儀、傅里葉紅外光譜儀、熱重分析儀、動態(tài)機械熱分析儀、偏光顯微鏡、掃描電子顯微鏡、萬能試驗機等測試手段對聚合物的結構、熱力學性能、表面形態(tài)、力學性能及自修復性能等進行了表征和分析,期望為具有良好力學性能和修復效果的交聯(lián)聚合物的開發(fā)提供新的思路。具體研究內(nèi)容如下:首先采用聚丙二醇二縮水甘油醚(ppgdge)及1-(3-氨基丙基)咪唑(api)以2:1的摩爾比反應得到含咪唑基團及端環(huán)氧基的二聚體,隨后通過zn~(2+)與咪唑形成配位鍵非共價交聯(lián),再利用4’4-二氨基二苯二硫醚(afd)為固化劑與環(huán)氧基團進行開環(huán)反應得到雙交聯(lián)網(wǎng)絡,同時合成了不含zn~(2+)-咪唑非共價交聯(lián)的可逆共價交聯(lián)網(wǎng)絡作為對比。利用核磁、紅外等手段證明了雙交聯(lián)網(wǎng)絡的化學結構。采用tga、dma、萬能試驗機等研究了雙交聯(lián)網(wǎng)絡的熱力學和力學性能。實驗結果表明非共價鍵的引入大大提高了聚合物的力學性能,循環(huán)拉伸測試說明了力學性能提高的原因在于非共價鍵對外力作用的能量耗散。利用偏光顯微鏡及萬能試驗機測試了雙交聯(lián)網(wǎng)絡在斷裂后的修復性能。實驗結果表明在高溫時,由于二硫鍵及金屬配位鍵均發(fā)生交換反應,所以雙交聯(lián)網(wǎng)絡及共價交聯(lián)網(wǎng)絡均表現(xiàn)出良好的修復性能。在溫度較低時,共價交聯(lián)網(wǎng)絡由于二硫鍵不能發(fā)生交換反應,所以不能進行修復,而雙交聯(lián)網(wǎng)絡由于非共價鍵的交換反應則恢復了部分力學性能,證明了非共價鍵有利于聚合物材料的自修復。重塑實驗則表明了雙交聯(lián)網(wǎng)絡及共價交聯(lián)網(wǎng)絡在徹底破壞后均能重復加工,達到降低材料使用成本的目的。其次,為充分發(fā)揮可逆共價(rcn)及可逆非共價(rncn)兩種交聯(lián)網(wǎng)絡的優(yōu)勢,制備了具有互穿網(wǎng)絡結構的聚合物(IPN),研究了RCN及RnCN在互穿網(wǎng)絡中所占含量不同對IPN性能的影響。采用SAXS和SEM等表征了IPN的結構,采用TGA、DMA及萬能試驗機等對其熱力學性能和自修復性能等進行了測試。結果表明:IPN的Tg介于RCN和Rn CN之間,說明兩者具有良好的相容性;SAXS的測試顯示IPN與RCN和RnCN出現(xiàn)同樣的規(guī)律,表明IPN并未發(fā)生微相分離;SEM也表明RCN與RnCN共混后形成了均一體系。循環(huán)拉伸試驗發(fā)現(xiàn),樣品受外力作用時,非共價交聯(lián)網(wǎng)絡首先受到破壞,而保證共價交聯(lián)網(wǎng)絡的完整,達到較好的增韌效果。純RCN的斷裂伸長率為44.1%,隨著Rn CN含量的增多,斷裂伸長率達200%。修復測試表明RCN修復48h后修復效率僅達80%左右,而IPN在同樣條件下修復12h,修復效率即可達90%以上。本章研究表明,將可逆共價及可逆非共價交聯(lián)網(wǎng)絡以互穿網(wǎng)絡的形式結合同樣可以起到增強力學性能及提高修復效率的目的。
[Abstract]:The intrinsic self-repairing materials based on reversible cross-linking reaction have become a research hotspot because they can repair materials spontaneously at the molecular level, prolong the service life of materials, broaden the application range of materials, and reduce the cost of materials. Compared with non-covalent crosslinking systems, compounds have better mechanical strength and are more suitable for the use of structural materials. A new class of self-repairing crosslinked polymers can be obtained by introducing reversible crosslinking reaction into covalent crosslinking polymers. However, reversible covalent bonds have less bond energy than traditional covalent bonds, which makes reversible crosslinking possible. It is a difficult problem to improve the strength of reversible crosslinked polymers without affecting their self-repairing effect. In order to improve the mechanical properties of materials, a method of introducing non-covalent bonds into materials as sacrificial bonds is often adopted by organisms. The covalent bond breaks first and consumes part of the energy to ensure that the material is not destroyed. The introduction of non-covalent bonds into reversible covalent crosslinked polymers by biomimetic method is expected to further improve their mechanical properties, but the reversibility of the non-covalent bond itself will not affect its self-healing effect. Based on coordination bonds, covalent and non-covalent crosslinked polymer networks and covalent crosslinked and non-covalent crosslinked interpenetrating networks were designed and synthesized to study the effect of the introduction of non-covalent bonds and the introduction of non-covalent crosslinking in reversible covalent crosslinking networks on reversible covalent crosslinked polymers. The structure, thermodynamic properties, surface morphology, mechanical properties and self-repairing properties of the polymer were characterized and analyzed by means of magnetic resonance, Fourier transform infrared spectroscopy, thermogravimetric analysis, dynamic mechanical thermal analysis, polarizing microscope, scanning electron microscope and universal testing machine. The specific research contents are as follows: firstly, the dimer containing imidazole group and epoxy-terminated group was synthesized by the reaction of polypropylene glycol diglycidyl ether (ppgdge) and 1 - (3-aminopropyl) imidazole (api) at the molar ratio of 2:1, and then non-covalent cross-linking of imidazole with Zn ~ (2 +) was formed. A reversible covalent crosslinking network without Zn ~ (2 +) - imidazole was synthesized by ring-opening reaction of 4'4-diaminodiphenyl disulfide (afd) with epoxy group as curing agent. The chemical structure of the network was proved by means of nuclear magnetic resonance and infrared spectroscopy. The thermodynamics and mechanical properties of the bi-crosslinking network were investigated. The results showed that the introduction of non-covalent bonds greatly improved the mechanical properties of the polymer. The cyclic tensile test showed that the reason for the improvement was the energy dissipation of the non-covalent bonds. The experimental results show that at high temperatures, disulfide bonds and metal coordination bonds exchange reactions, so the double cross-linking network and covalent cross-linking network show good repair performance. At low temperatures, covalent cross-linking network can not be repaired because disulfide bonds can not exchange reactions, but double cross-linking. The network restored some mechanical properties due to the exchange reaction of non-covalent bonds, which proved that non-covalent bonds were conducive to self-repairing of polymer materials. The remodeling experiments showed that both the bi-crosslinking network and the covalent crosslinking network could be reprocessed after being completely destroyed, so as to reduce the cost of material use. Secondly, in order to give full play to the reversible covalent network. Polymers (IPN) with interpenetrating network structure were prepared by using valence (rcn) and reversible non-covalence (rncn) crosslinking networks. The effects of different contents of RCN and RnCN in IPN on the properties of IPN were studied. The structure of IPN was characterized by SAXS and SEM, and its thermodynamic properties and self-repairing properties were characterized by TGA, DMA and universal testing machine. The results show that the Tg of IPN is between RCN and RnCN, indicating that they have good compatibility; SAXS test shows that IPN and RCN and RnCN have the same rule, indicating that IPN does not have microphase separation; SEM also shows that the blend of RCN and RnCN forms a homogeneous system. The breaking elongation of pure RCN was 44.1%. With the increase of Rn CN content, the breaking elongation reached 200%. The repair test showed that the repair efficiency of RCN was only about 80% after 48 hours, while that of IPN was about 12 hours under the same conditions. The research in this chapter shows that the combination of reversible covalent and reversible non-covalent crosslinking networks in the form of IPN can also enhance the mechanical properties and improve the repair efficiency.
【學位授予單位】：東華大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TB381
本文編號：2205597
[Abstract]:The intrinsic self-repairing materials based on reversible cross-linking reaction have become a research hotspot because they can repair materials spontaneously at the molecular level, prolong the service life of materials, broaden the application range of materials, and reduce the cost of materials. Compared with non-covalent crosslinking systems, compounds have better mechanical strength and are more suitable for the use of structural materials. A new class of self-repairing crosslinked polymers can be obtained by introducing reversible crosslinking reaction into covalent crosslinking polymers. However, reversible covalent bonds have less bond energy than traditional covalent bonds, which makes reversible crosslinking possible. It is a difficult problem to improve the strength of reversible crosslinked polymers without affecting their self-repairing effect. In order to improve the mechanical properties of materials, a method of introducing non-covalent bonds into materials as sacrificial bonds is often adopted by organisms. The covalent bond breaks first and consumes part of the energy to ensure that the material is not destroyed. The introduction of non-covalent bonds into reversible covalent crosslinked polymers by biomimetic method is expected to further improve their mechanical properties, but the reversibility of the non-covalent bond itself will not affect its self-healing effect. Based on coordination bonds, covalent and non-covalent crosslinked polymer networks and covalent crosslinked and non-covalent crosslinked interpenetrating networks were designed and synthesized to study the effect of the introduction of non-covalent bonds and the introduction of non-covalent crosslinking in reversible covalent crosslinking networks on reversible covalent crosslinked polymers. The structure, thermodynamic properties, surface morphology, mechanical properties and self-repairing properties of the polymer were characterized and analyzed by means of magnetic resonance, Fourier transform infrared spectroscopy, thermogravimetric analysis, dynamic mechanical thermal analysis, polarizing microscope, scanning electron microscope and universal testing machine. The specific research contents are as follows: firstly, the dimer containing imidazole group and epoxy-terminated group was synthesized by the reaction of polypropylene glycol diglycidyl ether (ppgdge) and 1 - (3-aminopropyl) imidazole (api) at the molar ratio of 2:1, and then non-covalent cross-linking of imidazole with Zn ~ (2 +) was formed. A reversible covalent crosslinking network without Zn ~ (2 +) - imidazole was synthesized by ring-opening reaction of 4'4-diaminodiphenyl disulfide (afd) with epoxy group as curing agent. The chemical structure of the network was proved by means of nuclear magnetic resonance and infrared spectroscopy. The thermodynamics and mechanical properties of the bi-crosslinking network were investigated. The results showed that the introduction of non-covalent bonds greatly improved the mechanical properties of the polymer. The cyclic tensile test showed that the reason for the improvement was the energy dissipation of the non-covalent bonds. The experimental results show that at high temperatures, disulfide bonds and metal coordination bonds exchange reactions, so the double cross-linking network and covalent cross-linking network show good repair performance. At low temperatures, covalent cross-linking network can not be repaired because disulfide bonds can not exchange reactions, but double cross-linking. The network restored some mechanical properties due to the exchange reaction of non-covalent bonds, which proved that non-covalent bonds were conducive to self-repairing of polymer materials. The remodeling experiments showed that both the bi-crosslinking network and the covalent crosslinking network could be reprocessed after being completely destroyed, so as to reduce the cost of material use. Secondly, in order to give full play to the reversible covalent network. Polymers (IPN) with interpenetrating network structure were prepared by using valence (rcn) and reversible non-covalence (rncn) crosslinking networks. The effects of different contents of RCN and RnCN in IPN on the properties of IPN were studied. The structure of IPN was characterized by SAXS and SEM, and its thermodynamic properties and self-repairing properties were characterized by TGA, DMA and universal testing machine. The results show that the Tg of IPN is between RCN and RnCN, indicating that they have good compatibility; SAXS test shows that IPN and RCN and RnCN have the same rule, indicating that IPN does not have microphase separation; SEM also shows that the blend of RCN and RnCN forms a homogeneous system. The breaking elongation of pure RCN was 44.1%. With the increase of Rn CN content, the breaking elongation reached 200%. The repair test showed that the repair efficiency of RCN was only about 80% after 48 hours, while that of IPN was about 12 hours under the same conditions. The research in this chapter shows that the combination of reversible covalent and reversible non-covalent crosslinking networks in the form of IPN can also enhance the mechanical properties and improve the repair efficiency.
【學位授予單位】：東華大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TB381
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