本文選題：補(bǔ)丁粒子 + 點(diǎn)擊聚合�。� 參考：《北京化工大學(xué)》2017年碩士論文

【摘要】：補(bǔ)丁粒子指具有一或多個(gè)不同化學(xué)或物理特性區(qū)域的粒子,補(bǔ)丁間或補(bǔ)丁與其他物質(zhì)間具有定向相互作用,使補(bǔ)丁粒子具有很多特殊功能和應(yīng)用,如用作多級結(jié)構(gòu)材料構(gòu)件、固體表面活性劑、藥物載體和傳感器等。目前,已發(fā)展出許多制備補(bǔ)丁粒子的方法。其中,種子溶脹-聚合相分離(種子相分離)法是應(yīng)用較為廣泛的一種方法,能夠大量制備補(bǔ)丁粒子,且粒子形貌易于調(diào)控。然而,該法涉及步驟較多,且補(bǔ)丁粒子各區(qū)域功能化較困難。本課題組將分散聚合過程中的增長粒子作為動態(tài)變化的種子,發(fā)展了一鍋(兩步、一步加料)分散聚合制備補(bǔ)丁粒子的方法,結(jié)合點(diǎn)擊反應(yīng),可調(diào)控補(bǔ)丁粒子新生成部分的形貌、結(jié)構(gòu)和組成,但沒有對該過程進(jìn)行系統(tǒng)研究。通常利用傳統(tǒng)自由基鏈增長聚合制備球形粒子及補(bǔ)丁粒子,最近幾年開始利用非均相逐步點(diǎn)擊聚合直接制備球形粒子,該法具有聚合條件溫和、粒子易于功能化等優(yōu)點(diǎn),但是所得粒子的Tg較低,且未涉及非球形或補(bǔ)丁粒子的制備。本論文在一鍋苯乙烯鏈增長分散聚合過程中結(jié)合巰基-烯逐步點(diǎn)擊聚合,制備形貌、結(jié)構(gòu)和組成可調(diào)控的補(bǔ)丁粒子,并探討所得粒子的功能化及應(yīng)用。論文主要工作如下:1.以甲醇/水(MeOH/H2O=6/4)混合液為分散介質(zhì),單體為苯乙烯(St)、苯乙烯磺酸鈉(NaSS),引發(fā)劑為偶氮二異丁腈(AIBN)進(jìn)行分散聚合。過程中加入巰基-烯點(diǎn)擊單體聚合,獲得了含有硬核(PSt,Tg較高)及軟殼層、單或多孔、單或多凸起(點(diǎn)擊聚合物,Tg較低)的粒子。探討了點(diǎn)擊單體加入時(shí)間、用量、配比及單體種類等對粒子形貌、結(jié)構(gòu)和組成的影響;2.通過SEM和TEM觀察、凝膠含量和轉(zhuǎn)化率測定及FTIR分析,考察了加入點(diǎn)擊試劑后粒子形貌、組成的演變過程及聚合行為。確定了補(bǔ)丁粒子的形成機(jī)理:PSt與點(diǎn)擊聚合物的Tg及親水性不同,導(dǎo)致分相、形成補(bǔ)丁粒子;等摩爾巰基-烯投料,發(fā)生非等摩爾反應(yīng),得到含過量-C=C-或-SH功能粒子;3.對補(bǔ)丁粒子不同區(qū)域進(jìn)行了選擇功能化:利用PSt核表面-SO3-負(fù)載磁性粒子,利用補(bǔ)丁處-SH吸附Ag納米粒子,利用補(bǔ)丁處-SH或-C=C-與功能單體點(diǎn)擊反應(yīng),得到熒光標(biāo)記補(bǔ)丁粒子、超疏水/親水粒子,進(jìn)一步獲得了超疏水/親水粒子膜。
[Abstract]:Patch particles are particles having one or more different regions of chemical or physical properties, and patches or patches have directional interactions with other substances, enabling patch particles to have many special functions and applications, such as being used as multilevel structural material components, Solid surfactants, drug carriers, sensors, etc. At present, many methods of preparing patch particles have been developed. Among them, seed swelling and polymeric phase separation (seed phase separation) is a widely used method, which can prepare patch particles in large quantities, and the morphology of the particles is easy to control. However, there are many steps involved in the method, and it is difficult to functionalize each region of patch particles. Our group developed a one-pot (two-step, one-step) dispersion polymerization method to prepare patch particles by using the growing particles in the dispersion polymerization process as seeds of dynamic change. The morphology, structure and composition of the newly formed part of the patch particles can be regulated, but no systematic study has been carried out on the process. Spherical particles and patched particles are usually prepared by traditional free radical chain growth polymerization. In recent years, spherical particles have been prepared directly by heterogeneous step by step click polymerization. This method has the advantages of mild polymerization conditions and easy functionalization of particles. However, the TG of the obtained particles is relatively low and does not involve the preparation of non spherical or patch particles. In this paper, in the process of one-pot styrene chain increasing dispersion polymerization, mercapto-alkene polymerization was combined step by step to prepare patched particles with adjustable morphology, structure and composition, and the functionalization and application of the resulting particles were discussed. The main work of this paper is as follows: 1. The dispersion polymerization was carried out with methanol / water / MeOH / H 2O 6 / 4 mixed solution as dispersion medium, monomer as styrene stout, sodium styrenesulfonate as sodium sulfonate and initiator as azodiisobutyronitrile (AIBN). In the process of mercapto-ene-click monomer polymerization, particles containing high hard core PSt-Tg and soft shell layer, single or porous, single or multiple protrusions (low TG of click-polymer) were obtained. The effects of click-monomer addition time, dosage, ratio and monomer type on particle morphology, structure and composition were discussed. The particle morphology, composition evolution and polymerization behavior were investigated by SEM and TEM, gel content and conversion and FTIR analysis. It was determined that the formation mechanism of patch particles was different from that of click-polymer and TG and hydrophilicity, which resulted in phase separation and formation of patch particles. Different regions of patch particles were selected and functionalized. Using magnetic particles loaded on the surface of PSt nucleus, adsorption of Ag nanoparticles by patch site -SH, click-to-click reaction between patch site and functional monomer, fluorescent labeled patch particles were obtained. Superhydrophobic / hydrophilic particle membranes were further obtained.
【學(xué)位授予單位】：北京化工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O631.5

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