本文選題：可熔融丙烯腈-丙烯酸甲酯共聚物(AN-MA) + 熱致相分離(TIPS)��； 參考：《天津工業(yè)大學(xué)》2017年碩士論文

【摘要】：聚丙烯腈(PAN)具有耐惰性溶劑、耐細(xì)菌侵蝕性、化學(xué)穩(wěn)定性好、機(jī)械性能優(yōu)良等特點(diǎn),已成為目前應(yīng)用非常廣泛的聚合物膜材料之一。PAN的結(jié)構(gòu)特殊,目前主要采用傳統(tǒng)的非溶劑致相分離(NIPS)工藝制備微孔膜。但是NIPS法制備PAN微孔膜往往需要大量的極性溶劑,造成溶劑的浪費(fèi)和環(huán)境污染,且制備的微孔膜力學(xué)性能較差。與傳統(tǒng)的NIPS工藝相比,熱致相分離(TIPS)工藝成膜過程更易控制,且制備的微孔膜力學(xué)性能較好。傳統(tǒng)的TIPS法采用單一的稀釋劑,由于單一的稀釋劑與聚合物組成的二元體系兩者間的相容性已經(jīng)固定,而稀釋劑與聚合物之間相容性的差異對微孔膜的結(jié)構(gòu)及性能有很大影響。本文分別選用碳酸乙烯酯(EC)與三甘醇二乙酸酯(TEGDA)和環(huán)丁砜(TMS)與碳酸二苯酯(DPC)組成兩種復(fù)配稀釋劑體系,通過調(diào)節(jié)復(fù)配稀釋劑間的比例調(diào)節(jié)其與AN-MA共聚物的相互作用力。單一的PAN均聚物膜較脆,實(shí)用性較差。本文采用柔性第二單體丙烯酸甲酯(MA)與丙烯腈(AN)共聚,削弱氰基間的偶極作用力,制備可熔融AN-MA共聚物,并以此為基體,采用TIPS法制備AN-MA微孔膜。本論文分為兩部分,首先,在TIPS成膜過程中引入溶膠凝膠(sol-gel)工藝,詳細(xì)研究了共聚物、稀釋劑、添加劑等對微孔膜結(jié)構(gòu)與性能的影響。然后,選擇結(jié)晶性的稀釋劑復(fù)配體系,詳細(xì)研究了成型溫度、共聚物、稀釋劑和添加劑對微孔膜結(jié)構(gòu)與性能的影響。實(shí)驗(yàn)結(jié)果發(fā)現(xiàn):以投料摩爾比為80/20的可熔融AN-MA共聚物(80/20 AN-MA)為基體,采用TIPS法sol-gel工藝制備80/20AN-MA微孔膜時,降低復(fù)配稀釋劑中EC含量和聚合物濃度,增加正硅酸乙酯(TEOS)的含量,均有利于膜水通量的提高。復(fù)配稀釋劑中EC含量為60 wt.%,聚合物濃度為9 wt.%,TEOS含量為5 wt.%時,AN-MA微孔膜的水通量最高可達(dá)120 L/(m2h);改變復(fù)配稀釋劑種類,制備了管狀孔和胞狀孔相間分布的80/20AN-MA共聚物微孔膜,分別添加羥基化碳納米管(MWNTs-OH)和埃洛石(HNTs),采用TIPS法制備了系列AN-MA微孔膜。研究發(fā)現(xiàn),膜斷面為兩種孔結(jié)構(gòu)相間分布的連通結(jié)構(gòu),當(dāng)MWNTs-OH添加入量為1 wt.%時,微孔膜的純水通量為563.7 L/(m2h);HNTS添加量為0.5 wt.%時,微孔膜的最大水通量為665.7 L/(m2h)。隨著鑄膜液體系中添加劑的加入,微孔膜的斷裂強(qiáng)度和柔韌有所增加。當(dāng)MWNTs-OH添加入量為3 wt.%,微孔膜的斷裂強(qiáng)度為3.7 MPa,斷裂伸長率為10%;HNTs添加量為1wt.%時,微孔膜的斷裂強(qiáng)度為2.6 MPa,斷裂伸長率為6%。
[Abstract]:Polyacrylonitrile (pan) has been widely used as one of the most widely used polymer membrane materials because of its inert solvent resistance, bacterial erosion resistance, good chemical stability and excellent mechanical properties. At present, the traditional non-solvent induced phase separation (NIPS) process is used to prepare microporous membranes. However, the preparation of pan microporous membranes by NIPS often requires a large number of polar solvents, resulting in waste of solvents and environmental pollution, and the mechanical properties of the prepared membranes are poor. Compared with the traditional NIPS process, the thermo-induced phase separation (TIPS) process is easier to control and the prepared microporous membranes have better mechanical properties. The traditional tips method uses a single diluent, because the compatibility between the single diluent and the polymer binary system has been fixed, and the difference of the compatibility between the diluent and the polymer has a great influence on the structure and properties of the microporous membrane. In this paper, two kinds of complex diluent systems are composed of ethylene carbonate (EC), triethylene glycol diacetate (TEGDA) and sulfolane sulfone (TMS320T) and diphenyl carbonate (DPC) respectively. The interaction force with AN-MA copolymers is adjusted by adjusting the proportion of the complex diluents. A single pan homopolymer film is brittle and less practical. In this paper, the flexible second monomer methyl acrylate (MAA) and acrylonitrile anhydride (ANN) were copolymerized to reduce the dipole force between cyanide groups and to prepare the meltable AN-MA copolymer. Based on this copolymer, AN-MA microporous membrane was prepared by tips method. This paper is divided into two parts. Firstly, the effects of copolymer, diluent and additive on the structure and properties of microporous membranes were studied by introducing sol-gel process into tips film forming process. Then, the effects of molding temperature, copolymer, diluent and additives on the structure and properties of microporous membranes were studied. The experimental results show that when 80 / 20AN-MA microporous films are prepared by tips sol-gel process, the EC content and polymer concentration in the composite diluent are decreased, and the content of tetraethyl orthosilicate (TEOS) is increased when the melt AN-MA copolymer with 80 / 20 molar ratio is used as the substrate, and 80 / 20 AN-MA microporous membrane is prepared by tips process. All of them are beneficial to the increase of membrane water flux. The maximum water flux of AN-MA microporous membrane was 120 L / m ~ (-2) h ~ (-1) when the concentration of polymer was 9 wt.and the concentration of polymer was 9 wt.The microporous membrane of 80 / 20 AN-MA copolymer with tubular pore and cellular pore phase distribution was prepared by changing the type of complex diluent, and the maximum water flux of the membrane was 120 L / m ~ (-2) h ~ (-1) when the concentration of TEOS was 5 wt.%. A series of AN-MA microporous membranes were prepared by tips method by adding hydroxylated carbon nanotubes (MWNTs-OH) and Ellostachys (HNTs) respectively. It is found that the cross-section of the membrane is a connected structure with the distribution of two pore structures. When the addition of MWNTs-OH is 1 wt.%, the pure water flux of the microporous membrane is 563.7 L / m ~ (2) h ~ (-1), the maximum water flux of the membrane is 665.7 L / m ~ (2) h. The fracture strength and flexibility of the microporous membrane increased with the addition of additives. When the addition amount of MWNTs-OH is 3 wt., the breaking strength of the microporous membrane is 3.7 MPA, the elongation at break is 10 wt.%, the fracture strength is 2.6 MPA and the elongation at break is 6 MPA.
【學(xué)位授予單位】：天津工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TQ051.893

【參考文獻(xiàn)】

相關(guān)期刊論文 前10條

1 邢天豪;羅春明;唐安斌;;PET/改性埃洛石納米管復(fù)合膜的制備與性能研究[J];西南科技大學(xué)學(xué)報;2015年01期

2 王爭爭;韓娜;陳素梅;張興祥;李偉;;熱致相分離法制備丙烯腈-丙烯酸甲酯/納米TiO_2復(fù)合膜及膜性能研究[J];中國科技論文;2014年12期

3 劉慧;周波;徐建明;陳慧闖;吁蘇云;方敏;;熱致相分離法制備聚偏氟乙烯中空纖維微孔膜的研究[J];浙江化工;2013年09期

4 劉敏;許振良;魏永明;趙龍寶;;低臨界共溶溫度PES體系制備微孔膜的研究[J];高校化學(xué)工程學(xué)報;2013年04期

5 車璇;王磊;孟曉榮;王旭東;呂永濤;;復(fù)合稀釋劑法制備聚偏氟乙烯超濾膜[J];水處理技術(shù);2013年07期

6 高英;秦愛文;李翔;馬博謀;何春菊;;埃洛石-聚醚砜復(fù)合膜的形態(tài)結(jié)構(gòu)及性能[J];功能高分子學(xué)報;2012年04期

7 馬智;王金葉;高祥;丁彤;秦永寧;;埃洛石納米管的應(yīng)用研究現(xiàn)狀[J];化學(xué)進(jìn)展;2012年Z1期

8 唐孝芬;韓娜;張榮;張興祥;;可熔融丙烯腈共聚物的組成及流變性與熱性能[J];高分子材料科學(xué)與工程;2011年12期

9 劉振;張珊;黃永福;李會軍;;混合稀釋劑對熱致相分離法制備聚偏氟乙烯微孔膜結(jié)構(gòu)的影響[J];功能材料;2011年06期

10 夏利國;;膜分離技術(shù)原理及在水處理行業(yè)中的應(yīng)用[J];山東化工;2010年09期

，

本文編號：2004469