本文選題：光聚合 + 聚丙烯腈　； 參考：《江南大學(xué)》2017年碩士論文

【摘要】：本論文建立了兩個(gè)新型的可見光引發(fā)聚合體系,實(shí)現(xiàn)了室溫條件下丙烯腈的原子轉(zhuǎn)移自由基聚合(ATRP)及無金屬自由基聚合反應(yīng),獲得了高分子量及窄分子量分布的聚丙烯腈(PAN),聚合過程操作簡單,反應(yīng)條件溫和,低能耗,對(duì)環(huán)境友好。詳細(xì)研究了聚合反應(yīng)行為及可能的聚合機(jī)理。實(shí)驗(yàn)具體內(nèi)容及結(jié)論如下:(1)室溫可見光照射下以α-溴芐基乙酸乙酯(EBPA)為引發(fā)劑,在光氧化還原催化劑Ir(ppy)3作用下實(shí)現(xiàn)了丙烯腈(AN)的ATRP反應(yīng)�？疾炝司酆象w系的不同組分對(duì)實(shí)驗(yàn)結(jié)果的影響,并在Ir(ppy)3的催化作用下獲得了高轉(zhuǎn)化率、高分子量及窄分布的PAN(95%,Mn.MA LLS8.0×104 g/mol,Mw/Mn1.30)。探究Ir(ppy)3催化的聚合體系動(dòng)力學(xué)行為,結(jié)果顯示該體系的聚合行為具有典型的“活性”特征。此外,實(shí)驗(yàn)以制備的聚丙烯腈(PAN-Br)為大分子引發(fā)劑,與丙烯酸丁酯(BA)進(jìn)行聚合合成了PAN-b-PBA嵌段共聚物�；诰酆闲袨榧熬酆袭a(chǎn)物的結(jié)構(gòu)對(duì)該反應(yīng)的機(jī)理進(jìn)行了推測(cè),推測(cè)該聚合機(jī)理為光引發(fā)的ATRP聚合。(2)室溫可見光照射下以芳基四氟硼酸重氮鹽為引發(fā)劑,在Eosin Y催化作用下實(shí)施AN無金屬自由基聚合反應(yīng),考察了不同條件對(duì)聚合反應(yīng)的影響,制得了高分子量及窄分子量分布的PAN(Mn,MALLS1.50×105 g/mol,Mn/Mw1.30)。實(shí)驗(yàn)在Eosin Y的催化體系下考察了AN的聚合行為,結(jié)果顯示聚合行為表現(xiàn)出一階線性動(dòng)力學(xué)關(guān)系、聚合產(chǎn)物分子量隨單體轉(zhuǎn)換率的增大而增大,且分子量分布較窄(Mn/Mw1.30)。此外,通過調(diào)節(jié)LED燈光源的“開/關(guān)”狀態(tài)可以調(diào)控聚合反應(yīng)的發(fā)生與停止。采用基質(zhì)輔助激光解吸電離-飛行時(shí)間質(zhì)譜(MALDI-TOF MS)和19F NMR對(duì)聚合產(chǎn)物的結(jié)構(gòu)進(jìn)行分析,結(jié)果表明聚合反應(yīng)是經(jīng)捕獲F-進(jìn)行氧化終止的,但以合成的PAN-F為大分子引發(fā)劑,沒能成功的實(shí)施擴(kuò)鏈反應(yīng),表明該體系下制備的PAN分子鏈存在一定程度上的“死鏈”。通過對(duì)該體系聚合行為的分析及聚合產(chǎn)物的表征,表明該聚合體系的活化/失活過程類似于光引發(fā)的ATRP聚合機(jī)理。(3)室溫可見光照射下以對(duì)氟苯基四氟硼酸重氮鹽(1a)為引發(fā)劑,在Eosin Y催化作用下實(shí)施衣康酸((IA)、丙烯酸甲酯(MA)、丙烯酸丁酯(BA)、苯乙烯(St)、丙烯酰胺(AM)五種單體分別與AN的共聚反應(yīng),實(shí)驗(yàn)均獲得了相應(yīng)的共聚產(chǎn)物。對(duì)AN/IA和AN/MA兩種共聚體系進(jìn)行了進(jìn)一步的研究,實(shí)驗(yàn)結(jié)果表明適量IA單體的加入不僅能提高聚合產(chǎn)物的分子量,制得高轉(zhuǎn)化率、高分子量及窄分布的P(AN-co-IA)(Conv.90%,Mn,MALLS1.70×105 g/mol,Mn/Mw1.30),且能有效的緩解集中放熱及在較低溫度下引發(fā)環(huán)化反應(yīng)。MA單體的加入對(duì)聚合產(chǎn)物分子量的影響不太,當(dāng)AN與MA的摩爾比值在85:15時(shí),差示掃描量熱儀(DSC)曲線上丙烯腈聚合物在187℃左右會(huì)出現(xiàn)一個(gè)熔融峰,在分解溫度(~315℃)之前。實(shí)驗(yàn)在AN/MA=85:15下考察了AN/MA的共聚行為,結(jié)果表明共聚行為呈現(xiàn)出一階的線性動(dòng)力學(xué)圖,聚合物的分子量隨分子量的增大而增大且保持分子量分布較窄(Mn/Mw1.30)。
[Abstract]:In this paper, two new visible light initiation polymerization systems have been established to achieve the atom transfer radical polymerization (ATRP) and free radical polymerization of acrylonitrile at room temperature. The polyacrylonitrile (PAN) with high molecular weight and narrow molecular weight distribution has been obtained. The polymerization process is simple, the reaction conditions are mild, the energy consumption is low, and the environment is friendly to the environment. The polymerization behavior and possible polymerization mechanism were studied in detail. The specific contents and conclusions were as follows: (1) the ATRP reaction of acrylonitrile (AN) was realized under the action of light oxidation-reduction catalyst Ir (PPy) (PPy) 3 under the visible light irradiation at room temperature. The experimental results of different components of the polymerization system were investigated. The high conversion, high molecular weight and narrow distribution of PAN (95%, Mn.MA LLS8.0 * 104 g/mol, Mw/Mn1.30) were obtained under the catalysis of Ir (PPy) 3. The kinetics of polymerization system of Ir (PPy) 3 catalyzed by Ir (PPy) 3 was investigated. The results showed that the polymerization behavior of the system had typical "activity" characteristics. In addition, the experiment was made of polyacrylonitrile (PAN-Br). PAN-b-PBA block copolymers were synthesized by polymerization of butyl acrylate (BA) for macromolecular initiator. Based on the polymerization behavior and the structure of the polymerization products, the mechanism of this reaction was speculated. It was deduced that the polymerization mechanism was light induced ATRP polymerization. (2) at room temperature visible light irradiation with aryl tetrafluoroboric acid diazonium as the initiator, Eosin Y Under the action of AN, the polymerization reaction of free radical polymerization was carried out. The effect of different conditions on the polymerization was investigated. The PAN (Mn, MALLS1.50 * 105 g/mol, Mn/Mw1.30) of the high molecular weight and narrow molecular weight distribution was prepared. The polymerization behavior of AN was investigated under the catalytic system of Eosin Y. The results showed that the polymerization behavior showed the first order linear dynamics. The molecular weight of the polymerization products increases with the increase of the monomer conversion rate, and the molecular weight distribution is narrow (Mn/Mw1.30). In addition, the polymerization reaction can be regulated by adjusting the "open / close" state of the LED lamp light source. The structure of the polymerization products by matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF MS) and 19F NMR The results showed that the polymerization was stopped by the capture of F-, but the synthesized PAN-F was a large molecular initiator, and the chain reaction was not successfully carried out. It showed that there was a certain "dead chain" in the PAN molecular chain prepared under the system. The activation / inactivation process of the polymerization system is similar to the photopolymerization mechanism of light induced ATRP. (3) under the room temperature visible light irradiation with fluoro phenyl tetrafluorboric acid diazonium (1a) as initiator, under the catalysis of Eosin Y, itaconic acid (IA), methyl acrylate (MA), butyl acrylate (BA), styrene (St), and acrylamide (AM) of the five monomers are in common with AN, respectively. The copolymerization products were obtained by the polymerization. The two copolymerization systems of AN/IA and AN/MA were further studied. The experimental results showed that the addition of appropriate IA monomers could not only improve the molecular weight of the polymerization products, produce high conversion rate, high molecular weight and narrow distribution of P (AN-co-IA) (Conv.90%, Mn, MALLS1.70 * 105 g/mol, Mn/Mw1.30). It can effectively alleviate the concentration of heat and the reaction of.MA monomer at lower temperature. The effect of the addition of.MA monomer on the molecular weight of the polymerization products is not very. When the molar ratio of AN to MA is at 85:15, the acrylonitrile polymer on the differential scanning calorimeter (DSC) curve will appear a melting peak at about 187 C, before the decomposition temperature (~315 C). The experiment is in AN. The copolymerization behavior of AN/MA was investigated under /MA=85:15. The results showed that the copolymerization behavior showed a first order linear kinetic diagram. The molecular weight of the polymer increased with the increase of molecular weight and kept the molecular weight distribution narrower (Mn/Mw1.30).
【學(xué)位授予單位】：江南大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O631.5

【參考文獻(xiàn)】

相關(guān)期刊論文 前10條

1 程衛(wèi)平;;聚丙烯腈基碳纖維在航天領(lǐng)域應(yīng)用及發(fā)展[J];宇航材料工藝;2015年06期

2 羅益鋒;羅晰e，

本文編號(hào)：2117617