原位实时近红外光谱研究核壳乳液聚合过程

将苯乙烯(St)和丙烯酸丁酯(BA)单体以不同的聚合方式制备核壳乳液和共聚乳液, 并采用近红外光谱技术实现了对乳液反应过程的原位实时监测, 通过对近红外光谱的谱带归属和主成分分析, 为近红外光谱技术判别乳液聚合过程提供了科学依据, 也为判断反向核壳乳液核壳翻转的拐点提出了一种新的方法. 采用簇类独立软模式法(SIMCA)建立了定性判别模型, 得到了很好的判别结果, 为进一步研究近红外光谱技术用于核壳乳液聚合过程奠定了基础.     

胶乳型互穿聚合物网络研究 Ⅰ.环氧树脂／聚丙烯酸酯半LIPN的制备

采用复合乳液聚合技术,合成了环氧树脂/聚(丙烯酸丁酯—苯乙烯—甲基丙烯酸甲酯)[EP/P(BA—St—MMA)]半胶乳型互穿聚合物网络(semi—LIPN),并探讨了反应温度、乳化剂用量、引发剂用量、不同单体配比、体系 pH 值、搅拌速度、EP 含量、交联剂种类及用量对聚合反应转化率及聚合稳定性的影响。     

光引发常规乳液聚合制备氨基聚苯乙烯纳米粒子

采用一种简单易行的方法制备了氨基功能化的聚苯乙烯纳米粒子.首先,采用4-乙烯基苄氯与1,3-丙二胺置换反应制备了含有氨基功能基团的可聚合单体N-(3-氨基丙基)对乙烯基苄基亚胺(CVPD).然后,采用乳液聚合,以苯乙烯(St)和CVPD为共聚单体,水溶性的4-(2-羟乙氧基)苯基-(2-羟基-2-丙基)酮(Irgacure 2959)为光引发剂,十六烷基三甲基溴化铵(CTAB)为乳化剂,经紫外光辐照引发,合成了P(St-co-CVPD)二元共聚物的纳米胶乳.体系的乳化剂用量仅为体系总质量的0.1 wt%～0.8 wt%,远小于常用来制备纳米粒子的微乳液体系的乳化剂用量.用透射电子显微镜(TEM)和激光粒度分析仪(DLS)表征了P(St-co-CVPD)纳米粒子的粒径和粒径分布.用红外光谱(FTIR)和核磁共振(NMR)证明了P(St-co-CVPD)纳米粒子上氨基的存在,并通过茚三酮显色反应定量检测了氨基含量.分别研究了单体配比,引发剂浓度,乳化剂用量以及紫外光强度对反应体系的影响.实验结果表明,产物粒子尺寸为30～600 nm,氨基通过共价键连接在粒子上,其含量为1.2×10-5～1.6×10-4 mol/g.该乳液体系聚合反应速率较快,单体转化率在60 min内即可达到80%.所得粒子的氨基含量可以通过单体配比进行调节.粒子尺寸可通过单体配比,引发剂浓度,乳化剂用量以及紫外光强度进行调节.     

纳米醋丙乳液的合成与性能表征

以醋酸乙烯酯(VAc)为原料,丙烯酸丁酯(BA)和丙烯酸(AA)为改性单体,过硫酸钾(KPS)为引发剂,OP-10,SDS和可聚合乳化剂丙烯氧基壬基酚聚氧乙烯(10)醚硫酸铵为乳化剂体系,采用半连续种子乳液聚合法制备了纳米粒径的醋丙乳液.对得到的乳液进行了分子量,热性能,红外光谱,乳液稳定性等测试,用激光散射粒度仪和透...     

反相乳液共聚合制备两性丙烯酰胺共聚物的研究

采用Span80-Tween80复合乳化剂和AIBA引发剂,进行丙烯酸钠(NaAA)/丙烯酰胺(AM)/丙烯酰氧基乙基三甲基氯化铵(DAC)反相乳液共聚合.研究了聚合温度、引发剂用量、单体浓度、共聚单体中DAC和AM含量、乳化剂用量及其HLB值、水/油比和水相pH值等聚合反应工艺条件或参数对聚合反应单体转化率和聚合物特性粘度的影响,聚合物特性粘度随引发剂用量和单体浓度的增大而增大的实验结果证实了该两性丙烯酰胺共聚物反相乳液制备过程中凝胶效应的存在.傅立叶红外光谱组成分析表明了两性丙烯酰胺共聚物的成功合成,扫描电镜观测乳胶粒粒径范围在0.6~8.0μm.     

可聚合乳化剂合成苯乙烯-丙烯酸丁酯-α-烯烃磺酸钠共聚物乳液

以工业原料α-烯烃磺酸钠(AOS)作为可聚合乳化剂,苯乙烯(St)和丙烯酸丁酯(BA)为单体,采用预乳化种子乳液聚合合成了St-BA-AOS共聚物乳液.通过测定AOS与两种单体的竞聚率确定了半连续加料法的聚合方式.探讨了单体的加料方式、反应温度、反应时间、AOS用量等工艺条件对胶乳的影响,获得了最佳聚合条件.IR,NMR和DSC测试结果分析表明:St,BA与AOS发生了自由基共聚反应,形成的P(St-BA-AOS)共聚物结构中含有磺酸基等亲水性基团有利于乳液的稳定.在此基础上考察了AOS用量对乳液的固含量及乳胶粒粒径等的影响.结果表明:随着AOS用量的增加,乳液的固含量增加、乳胶粒的平均粒径减少.当AOS含量为2%时乳液的固含量为45.01%,平均粒径为74 nm,粒径分布指数为0.08,玻璃化温度为23.17℃.TEM测试结果显示,用相同量的AOS代替十二烷基硫酸钠可得到粒径更小和粒径分布更为均匀的乳液体系.     

有机硅氧烷改性St/BA/AA三元共聚乳液的制备

采用核壳乳液聚合法,制备了乙烯基三乙氧基硅烷（VTES）改性的St/BA/AA三元共聚乳液,其结构经FT IR确证。研究了VTES用量、乳化剂用量及配比和引发剂用量对单体转化率和粒径的影响。结果表明：在最优条件［48%St, 48%BA, 4%AA, 1%N-MA, 4%VTES, 8%乳化剂（OP-10/SDS=1/3）, 0.8%引发剂］下,单体转化率为95.8%,平均粒径242 nm。并研究了改性St/BA/AA乳胶膜(1)的耐溶剂性和铅笔硬度。结果表明：1具有良好的耐溶剂性,铅笔硬度为2H。     

正交实验法优化氟硅丙乳液的制备工艺

利用L25(56)正交实验设计方法,研究了引发剂,乳化剂,有机硅、氟的用量以及聚合温度,单体配比等因素对乳液单体转化率的影响.在本实验条件下,得出制备氟硅丙乳液的最佳工艺条件为:乳化剂用量为4%,引发剂用量为ω=0.6%,单体配比为n(BA):n(MMA)=44:54,有机硅用量ω=10%,有机氟用量ω=4%,聚合温度...     

高固含量丙烯酸酯的微乳液聚合

采用半连续滴加预乳液的微乳液聚合法,合成出聚合物质量分数40%、乳化剂质量分数2.5%的丙烯酸酯微乳液. 考察了单体滴加速度、乳化剂种类及其用量、电解质用量、温度和搅拌等因素对乳液粒径及性能的影响. 研究表明,聚合在相当于Winsor-Ⅰ型的聚合体系中进行,由纯单体相(滴入的单体)和O/W微乳相构成,上层单体只起储存库的作用,它在缓慢的搅拌帮助下扩散进入微乳相中,只要微乳液液面上补加的单体不扰动微乳液的平衡,即不会产生粗粒子. 单体滴加时间控制在4 h,选择质量分数为2.5%的Dowfax2A1/OP-10乳化体系,NaHCO3质量分数为0.16%,反应温度控制在75～80 ℃,搅拌速度控制在150 r/min,可使聚合反应平稳进行,得到了m(聚合物)∶m(乳化剂)=15∶1的丙烯酸酯微乳液.     

水性涂料用聚丙烯酸酯微乳液的合成及其表征

低污染、低能耗的乳液涂料在建筑涂料中得到了广泛应用,具有核壳结构的聚合物乳液对胶膜的力学性能有较大的改善[1],微米(或纳米)级乳液具有优异的成膜性能,两者均是近年来高分子材料科学中发展十分迅速的新领域[2]。但微乳液聚合时乳化剂用量大,单体含量少。本文采用阴非离子复合乳化剂体系,单体预乳化工艺,种子乳液聚合法,通过正交实验优化聚合工艺参数及体系配方,合成了纳米级聚丙烯酸酯微乳液。并对乳液聚合物的粒径及分布、热性能、分子量及分布、结构等进行了表征。1　实验部分1 1　主要原料及乳液表征苯乙烯(St)、甲基丙烯酸甲…     

In Line Monitoring of VAc-BuA Emulsion Polymerization Reaction in a Continuous Pulsed Sieve Plate Reactor using NIR Spectroscopy

Summary: This work deals with the in line and in situ monitoring of the changes in residual monomer concentrations and polymer particle size in the process of emulsion copolymerization of vinyl acetate (VAc) and butyl acrylate (BuA) over the sections of a novel tubular reactor (pulsed sieve plate continuous reactor, PSPC) using NIR spectroscopy. Off-line measurements (gas chromatographic, gravimetric and dynamic light scattering) were used as reference for the development of the multivariate PLS calibration model. All NIR spectra were on-line collected with an IFS 28/N Bruker spectrometer using a probe (transflectance mode) immersed into the reaction medium. The calibration model and validation data were analyzed using the OPUS/QUANT software. The results indicated that there exists a good agreement between values from the NIR calibration models and the off-line reference measured experimental data. Moreover, the on-line NIR can detect efficiently the occurrence of disturbances during the polymerization reaction, a useful tool for the improving the process safety.     

反应性乳化剂存在下的五元苯丙乳液共聚合

采用反应性乳化剂SE-10N,通过正交实验及单因素实验确定了以苯乙烯、甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸和丙烯腈为单体的五元无皂苯丙共聚乳液的组成及聚合工艺。所制得的无皂乳液稳定,其乳胶粒大小均匀,粒径为50~60nm,比同组成的有皂乳液乳胶粒的粒径稍小。乳液涂膜透明、硬度达H级;其硬度、耐水性及钙离子稳定性均较同组成有皂乳液的好。     

St-BA copolymer emulsions prepared by using novel cationic maleic dialkyl polymerizable emulsifier

A novel polymerizable cationic dialkyl maleic emulsifier with 12 carbon atomic hydrophobic chain lengths (R = C₁₂H₂₅) as well as a similar conventional cationic emulsifier, cetyltrimethyl ammonium bromide (CTAB) as comparison, were investigated in batch emulsion copolymerization of styrene and butyl acrylate. A series of emulsion samples have been prepared with two kinds of emulsifiers, and their properties have been characterized and compared. Compared with the emulsions prepared by using cationic CTAB emulsifier, the emulsions prepared by using maleic emulsifier have larger particle size, higher surface tension, generally more stable on certain electrolytes and less water absorption ratio as 34.87% after 30 days vs. 50.65% for the emulsion containing CTAB emulsifier. Whereas, the maleic emulsifier itself has lower CMC and surface tension compared with cationic CTAB emulsifier.     

Preparation and Characterization of Polymer Core Shell Latex Particles

Stable core‐shell latex was synthesized by semicontinuous seeded emulsion polymerization with core monomers consisting of styrene (St), butyl acrylate (BA), and shell monomers consisting of methyl methacrylate (MMA), eutyl acrylate (EA), and methacrylic acid (MAA). The effects of compound emulsifier amount, mass ratio of anionic/nonionic emulsifier, and initiator amount on latex performance were investigated. By particle size analysis and transmission electron microscopy (TEM) observation, results suggest that final latex particles have clearly core shell structures.     

An Emulsifier‐Free RAFT‐Mediated Process for the Efficient Synthesis of Cerium Oxide/Polymer Hybrid Latexes

Hybrid latexes based on cerium oxide nanoparticles are synthesized via an emulsifier‐free process of emulsion polymerization employing amphiphatic macro‐RAFT agents. Poly(butyl acrylate‐co‐acrylic acid) random oligomers of various compositions and chain lengths are first obtained by RAFT copolymerization in the presence of a trithiocarbonate as controlling agent. In a second step, the seeded emulsion copolymerization of styrene and methyl acrylate is carried out in the presence of nanoceria with macro‐RAFT agents adsorbed at their surface, resulting in a high incorporation efficiency of cerium oxide nanoparticles in the final hybrid latexes, as evidenced by cryo‐transmission electron microscopy.     

壳多糖与丙烯酸丁酯的乳液接枝共聚研究

以十二烷基苯磺酸钠为乳化剂，过硫酸钾－亚硫酸氢钠为引发剂，研究了壳多糖与丙烯酸丁醋的乳液共聚合，结果表明当［Ｋ２Ｓ２Ｏ８］＝［ＮａＨＳＯ３］＝２．５７×１０－３ｍｏｌ·１－１，［ＢＡ］＝０．６８ｍｏｌ．１－１，［Ｃｈｉｔｏｓａｎ］＝１９．２ｇ·ｌ－１，在７０℃下反应５小时，共聚反应的接技率和接枝效率均较高．用红外光谱，差热分析，Ｘ射线衍射，扫描电镜对接技共聚物进行了表征，此外测试了共聚物胶乳成膜的机械性能，表明用丙烯酸丁酯对壳多糖进行接枝改性，可提高壳多糖的韧性，扩大其应用范围．     

氧化-还原低温引发苯乙烯/丙烯酸丁酯细乳液聚合粒度分布和成核机理的研究

用氧化还原引发剂(NH₄)₂S₂O₈/NaHSO₃研究了苯乙烯(St)/丙烯酸丁酯(BA)低温下的细乳液共聚合,细乳液单体液滴在亚微米级(100～400nm).测定了聚合过程中粒子大小及分布的变化,发现细乳液聚合随引发剂、乳化剂和共乳化剂浓度的增加,乳胶粒子尺寸变小,分布变宽,并且比相同条件下传统乳液聚合的粒子大.计算了聚合过程中粒子数变化规律及乳化剂覆盖率,讨论了细乳液与传统乳液中引发剂、乳化剂对反应过程的影响及成核机理的差异.     

K2S2O8/Na2SO3引发St/BA微乳液共聚合的研究

以十二烷基硫酸钠／十二烷基苯磺酸钠(SDS／SDBS)为乳化剂，过硫酸钾／亚硫酸钠(K2S2O3／Ni2SO3)为引发剂进行苯乙烯／丙烯酸丁酯(SL／BA)微孔液共聚合反应。研究了引发剂浓度[I]OR、单体总浓度[M]、乳化剂含量[E]和聚合温度T对微孔液共聚合最大反应速率Rmax和共聚物粘均分子量^-Mη的影响，测定了共聚单体的竞聚率，结果得到：Rmax∝[I]^0.98OR[M]^0.81[E]^-0．34e^-4712／T，^-Mη∝[I]^-0.27OR[M]^0.48[E]^-0.68e^2304/T；rSt=0.598，rBA=0.0206。