(n-BuCp)_2TiCl_2/Sn/I_s引发合成梳形羟基功能化无规聚苯乙烯及聚合物结构与性能的研究

采用茂金属化合物(n-BuCp)2TiCl2,还原剂(Sn),引发剂苯基缩水甘油基醚甲醛共聚物(Is)组成的催化体系引发苯乙烯活性自由基聚合,合成梳形羟基功能化无规聚苯乙烯.考察了聚合温度、聚合时间及引发剂与单体的比例对苯乙烯聚合的影响.当聚合温度在65～95℃范围内,随着聚合温度的升高,聚合物的分子量及单体转化率增加;在一定温度下,聚合物的分子量与单体转化率之间存在线性增长关系,且聚合物的分子量分布较窄(Mw/Mn=1.6～1.9).采用GPC,WAXD,13C(1H)-NMR对聚合物(沸丁酮可溶级分)的结构与性能进行了表征.GPC结果证明(n-BuCp)2TiCl2/Sn/Is引发苯乙烯聚合为活性聚合;13C-NMR和WAXD结果说明聚苯乙烯链段为无规结构;1H-NMR结果表明聚合物分子链中含有羟基,并根据其结果计算出聚合物分子的臂数为4,与引发剂Is的环氧基团数相等.这些结果证明了其聚合机理是经环氧基团开环后形成的自由基引发苯乙烯自由基聚合.     

悬浮-乳液复合聚合聚苯乙烯-聚甲基丙烯酸甲酯复合粒子的颗粒特性和成粒机理

采用在苯乙烯 (St)悬浮聚合过程中滴加甲基丙烯酸甲酯 (MMA)乳液聚合组分的悬浮 乳液复合聚合方法 ,制备大粒径聚苯乙烯 聚甲基丙烯酸甲酯 (PS PMMA)复合粒子 .研究聚合物粒径分布和颗粒形态的变化发现 ,在St悬浮反应中期滴加MMA乳液聚合组分后 ,聚合体系逐渐由悬浮粒子与乳胶粒子并存向形成单峰分布复合粒子转变 ,最终形成核 壳结构完整的大粒径PS PMMA复合粒子 ;在St悬浮反应初期滴加MMA乳液聚合组分 ,St与MMA一起分散成更小液滴 ,反应后期凝并成非核 壳结构复合粒子 ;在St悬浮反应后期滴加MMA乳液聚合组分 ,PMMA乳胶粒子与PS悬浮粒子基本独立存在 .根据以上结果 ,提出了St MMA悬浮 乳液复合聚合的成粒机理 .     

微乳液聚合耦合共混法构建聚偏氟乙烯共混杂化膜

以苯乙烯和甲基丙烯酸甲酯混合物作为油相, 采用反相微乳液法制备了AgCl纳米粒子; 通过微乳液原位聚合油相单体得到包含AgCl纳米粒子的聚合乳液; 将聚合乳液与聚偏氟乙烯(PVDF)通过共混法构建了包含AgCl纳米粒子的PVDF共混杂化膜. 紫外-可见光谱、 透射电子显微镜(TEM)及扫描电子显微镜(SEM)等表征结果和超滤实验结果表明, 聚合乳液加入的同时引入了亲水性聚合物和表面亲水的AgCl纳米粒子, 不仅改善了PVDF共混杂化膜的孔隙率和平均孔径, 还显著增强了PVDF共混杂化膜的极性和亲水性, 最终提升了膜的水通量和抗污染性能; 过量聚合乳液加入后不能与PVDF材料均匀共混, 而且AgCl纳米粒子也会在膜中形成团聚物堵塞膜孔隙, 从而削弱了膜的水通量和抗污染性能.     

超浓乳液聚合制备PU/PS的SIPN粉状树脂研究

将聚氨酯予聚体 (PU ) 苯乙烯 (St)的复合体系 ,用超浓乳液聚合方法制备了半互穿聚合物网络(SIPN)复合聚合物 ,得到了用聚氨酯予聚体改性的聚苯乙烯 (PU/PS)SIPN粉状树脂 .研究了分散相的比例(α)和聚合温度对聚合稳定性及聚合转化率 -时间的关系 ;测定了聚合物胶乳粒子的大小、形态 ,玻璃化温度 ,动态力学性能等 .结果表明 ,超浓乳液聚合较之本体聚合具有较高的聚合速率 ,容易控制所制备的胶乳粒径 ,能够制得PU/PS复合聚合物的SIPN粉状树脂 .该粉状树脂便于加工 ,具有良好的强韧性 ,有利于扩大应用     

“活”的α-甲基苯乙烯共聚物:聚合反应新化学和材料工程新技术

高于临界聚合反应温度时,α-甲基苯乙烯(AMS)单体和其聚合物处于聚合-解聚平衡.基于AMS聚合物在受热时可裂解生成大分子链自由基的特性,提出了含AMS结构单元的共聚物是一种"活"的,可作为大分子自由基引发剂的概念,并通过实验对AMS共聚物的引发性能和应用进行了研究.首先,合成了AMS与(甲基)丙烯酸酯类单体、丙烯酸、苯乙烯和马来酸酐等的共聚物.然后以上述共聚物为大分子引发剂,在90℃引发(甲基)丙烯酸酯类单体和苯乙烯等的本体聚合、溶液聚合和乳液聚合,得到了嵌段共聚物.用ESR谱证明了AMS的共聚物在加热时能裂解生成以碳原子为中心的大分子链自由基.此外,在聚合物的熔融共混中,AMS分解产生的大分子链自由基通过偶合反应形成接枝链,原位生成相容剂.AMS共聚物还可以对碳纳米管及无机粒子进行表面原位接枝改性.AMS共聚物是一类无小分子残留的绿色自由基引发剂,可以用于低成本制备两嵌段共聚物,也可以用于聚合物的熔融共混增容.     

基于2,5-二(4''''-甲酰基苯基)苯乙烯的螺旋链光学活性聚合物的合成与表征

通过2,5-二溴苯乙烯与对甲酰基苯硼酸的Suzuki偶联反应得到2,5-二(4'-甲酰基苯基)苯乙烯.在催化剂量的冰乙酸存在下,与光学纯的(S)-(-)-α-甲基苄胺或(R)-( )-α-甲基苄胺发生缩和反应,得到了一对手性非外消旋单体,( )-2,5-二{4'-[(N-(S)-α-甲基苄亚胺基)次甲基]苯基}苯乙烯和(-)-2,5-二{4'-[(N-(R)-α-甲基苄亚胺基)次甲基]苯基}苯乙烯.以偶氮二异丁腈(AIBN)或过氧化苯甲酰(BPO)为引发剂,经自由基溶液聚合得到光学活性聚合物.比旋光度、紫外-可见吸收光谱以及圆二色光谱研究表明,聚合物主链可能形成了某一方向占优的稳定螺旋构象,且该螺旋构象的旋光方向与单体的旋光方向相反.聚合条件对聚合物的光学活性有很大影响,在极性较大的芳香族溶剂和较高温度下得到的聚合物具有和单体相差更大的比旋光度.侧基的手性基团脱除后,聚合物仍具有一定的旋光性,说明聚合过程中形成的螺旋手性具有一定的记忆效应.     

双-(β-酮萘胺)镍(Ⅱ)/MAO催化剂体系催化苯乙烯聚合

 采用双-(β-酮萘胺)镍(Ⅱ)为主催化剂,以甲基铝氧烷(MAO)为助催化剂,在甲苯溶剂中进行了苯乙烯聚合实验,并考察了聚合温度、Al/Ni摩尔比、单体浓度和聚合时间等因素对聚合反应的影响. 结果表明,双-(β-酮萘胺)镍(Ⅱ)/MAO催化剂显示出很高的催化活性,可催化苯乙烯聚合得到中等分子量和分子量分布较窄(Mw/Mn＜1.6)的聚苯乙烯. 采用核磁共振氢谱、核磁共振碳谱、傅里叶变换红外光谱、差示扫描量热法和广角X射线衍射技术对聚合产物进行了表征. 结果表明,所得聚合物为无规聚苯乙烯.     

基于2,5-二(4′-甲酰基苯基)苯乙烯的螺旋链光学活性聚合物的合成与表征

通过2,5-二溴苯乙烯与对甲酰基苯硼酸的Suzuki偶联反应得到2,5-二(4′-甲酰基苯基)苯乙烯.在催化剂量的冰乙酸存在下,与光学纯的(S)-(-)-α-甲基苄胺或(R)-(+)-α-甲基苄胺发生缩和反应,得到了一对手性非外消旋单体,(+)-2,5-二{4-′[(N-(S)-α-甲基苄亚胺基)次甲基]苯基}苯乙烯和(-)-2,5-二{4′-[(N-(R)-α-甲基苄亚胺基)次甲基]苯基}苯乙烯.以偶氮二异丁腈(AIBN)或过氧化苯甲酰(BPO)为引发剂,经自由基溶液聚合得到光学活性聚合物.比旋光度、紫外-可见吸收光谱以及圆二色光谱研究表明,聚合物主链可能形成了某一方向占优的稳定螺旋构象,且该螺旋构象的旋光方向与单体的旋光方向相反.聚合条件对聚合物的光学活性有很大影响,在极性较大的芳香族溶剂和较高温度下得到的聚合物具有和单体相差更大的比旋光度.侧基的手性基团脱除后,聚合物仍具有一定的旋光性,说明聚合过程中形成的螺旋手性具有一定的记忆效应.     

自稳定沉淀聚合原理、方法及应用

经多年系统研究,本课题组开发了一种新型非均相聚合方法——"自稳定沉淀聚合"技术.与传统乳液/悬浮/分散聚合不同,该聚合体系不使用任何稳定剂,通过静态聚合及自成核-表面沉积增长过程,形成由粒径均匀的聚合物粒子和分散介质构成的稳定胶体;经简单的自沉降、过滤或离心分离,即可得到纯净的聚合物产品,分离出的上清液可用于下次聚合,无后处理问题,具有"绿色聚合工艺"优点.该聚合新方法简单高效,具有以下特点:(1)所制备聚合产物形貌尺寸均匀可控;(2)通过α-烯烃-马来酸酐交替共聚合,提高烯烃单体自由基聚合的活性;(3)特别是可用于混合烯烃单体聚合,制备多元共聚物粒子,为巨量烯烃资源的利用提供新途径.     

苯乙烯微乳液种子聚合

通过观测苯乙烯微乳液种子聚合前后体系内聚合物粒子大小及其分布的变化发现,无论是γ射线还是KPS引发,聚合过程中都没有新的聚合物粒子生成。尽管聚合前体系中存在单体溶胀的胶束,但在聚合过程中这些胶束主要充当单体仓库,自己成核聚合的几率很低。由于微乳液种子聚合体系内,单体量相对较低,聚合物粒子数目很大,其聚合动力学明显不同于常规乳液种子聚合。     

苯乙烯-甲基丙烯酸甲酯悬浮-乳液复合聚合过程中聚合物复合粒子组成的变化

采用苯乙烯(St)悬浮聚合过程中滴加甲基丙烯酸甲酯(MMA)乳液聚合组分,悬浮乳液复合聚合(SECP)方法,制备大粒径聚苯乙烯聚甲基丙烯酸甲酯(PS- PMMA)复合粒子.采用FTIR、1H- NMR、13C- NMR分析方法,研究SECP各个时期复合粒子中MMA- St链节摩尔比,发现悬浮粒子中MMA St链节摩尔比逐渐增大,而PMMA乳胶粒子中逐渐减少,表明悬浮相和乳液相间存在物质传递过程.悬浮粒子中MMA链节质量与MMA总投料质量比主要由乳胶粒子生成速率和乳胶粒子向悬浮粒子凝聚速率决定.最终得到的复合粒子除含PS和PMMA均聚物外,还含少量MMA-St共聚物.     

Synthesis and Characterization of β‐CD‐Coated Polystyrene Microspheres by γ‐Ray Radiation Emulsion Polymerization

Polystyrene (PS) microspheres coated with β‐cyclodextrin (β‐CD) were fabricated via γ‐ray‐induced emulsion polymerization in a ternary system of styrene/β‐CD/water (St/β‐CD/water). The solid inclusion complex of St and β‐CD particles formed at the St droplets–water interface can stabilize the emulsion as the surfactant. TEM and XPS results showed that β‐CD remains on the surface of PS particles. The average size of the PS particles increases from 186 to 294 nm as the weight ratio of β‐CD to St rises from 5% to 12.5%. The water contact angle (CA) of PS latex film is lower than 90°, and reduces with the β‐CD content even to 36°. Thus, this work provides a new and one‐pot strategy to surface hydrophilic modification on hydrophobic polymer particles with cyclodextrins through radiation emulsion polymerization.     

Emulsion polymerization of styrene and methyl methacrylate using a hydrophobically modified inulin and comparison with other surfactants

The use of a new class of graft polymer surfactants, based on inulin, in emulsion polymerization of poly(methyl methacrylate) (PMMA) and polystyrene (PS) particles is described. PS and PMMA were synthesized by emulsion polymerization, and stable particles with a high monomer content (50 wt %) were obtained with a very small amount of polymeric surfactant ([surfactant]/[monomer] = 0.0033). The latex dispersions were characterized by dynamic light scattering and by transmission electron microscopy to obtain the average particle size and the polydispersity index, and the stability was determined by turbidimetry measurements and expressed in terms of critical coagulation concentration. The last section gives a comparison of PMMA particles prepared by emulsion polymerization using classical surfactants from different types as emulsifiers with that obtained using the copolymer surfactant. It shows the superiority of INUTEC SP1 as it is the only one that allows stable particles at 20 wt % monomer content, with a smaller ratio [surfactant]/[monomer] = 0.002.     

粒径可控阳离子型聚苯乙烯纳米粒子的制备及表征

在采用阳离子型双子（gemini）表面活性剂作为乳化剂,不使用任何助乳化剂的条件下,通过改进微乳液聚合工艺制备了窄分布粒径可控的阳离子型聚苯乙烯（PS）纳米乳液。 改进微乳液聚合的主要特点是：大部分苯乙烯以预乳液的形式恒速滴入引发聚合的微乳液中,使用具有高乳化性能的gemini表面活性剂作为乳化剂能明显降低乳胶粒粒径。 实验结果表明,少量阳离子单体三甲基烯丙基氯化铵作为共聚单体能够明显减小Z均粒径、降低粒度分布,乳化剂用量、引发剂用量和反应温度均能影响制备乳胶粒的粒径及其粒度分布。 乳化剂和引发剂用量分别为苯乙烯质量的5%~10%和1.0%~1.5%、反应温度为70~75 ℃时,能够制备粒径小分布窄的阳离子型聚苯乙烯纳米粒子。 Z均粒径与苯乙烯质量之间的线性关系表明,Z均粒径可以通过苯乙烯用量来控制。 不同聚合工艺下制备的聚合物粒度分布曲线表明,改进微乳液聚合工艺（半连续预乳化工艺）在制备窄分布的聚合物纳米粒子方面具有很强的优越性。     

Preparation of polystyrene particles with narrow particle size distribution by γ-ray initiated miniemulsion polymerization stabilized by polymeric surfactant

Co-60 γ-ray initiated miniemulsion polymerization of styrene stabilized by an alkali soluble polymeric surfactant (ASPS) was studied in this work. The affecting factors, including absorbed dose, dose rate, surfactant concentration, and hexadecane (HD) concentration, were systematically studied. The particle size and particle size distribution (PSD) of final latexes was determined by transmission electron microscope (TEM). The results indicated that polystyrene (PS) particles with narrow PSD could be easily prepared by this method, and the particle size could be controlled from 50 nm to 250 nm by adjusting the concentration of HD and ASPS. HD concentration, surfactant concentration, dose rate and total absorbed dose strongly affected the particle size and PSD of PS latexes.     

颗粒内受限聚合法制备PP/POE/PS合金

以等规聚丙烯/乙烯-辛烯共聚物(PP/POE)合金颗粒为扩散基体, 苯乙烯(St)为扩散单体, 利用颗粒内受限聚合法制备了PP/POE/PS三元合金. 结果表明, 对于POE质量分数为20%~40%的PP/POE合金颗粒, St均可扩散至直径为4 mm的颗粒中心部位, 在POE非晶相中生成相尺寸为几十至几百纳米的PS球. 在PP/POE合金颗粒的不同部位, 因POE相尺寸及单体的吸附量不同, 生成的PS相尺寸也不同, 在颗粒中心部位生成的PS球最小. 研究了St在PP/POE(质量比80: 20)颗粒中的扩散-聚合行为, 结果表明, St在合金颗粒中的扩散速率和扩散饱和值远大于在纯PP颗粒中的扩散速率和饱和值, 这主要是因为PP/POE合金颗粒中的非晶POE相有利于扩散. 改变单体投料量可以获得具有不同PS含量的PP/POE/PS三元合金. 结晶性能研究结果表明, PS在非晶POE相中的优先分布会使POE相体积增大, 从而使PP的结晶温度和熔融温度降低. 随着PS量的进一步增大, 分布在PP中的PS对PP有结晶成核作用.     

Morphology and grafting in polybutylacrylate-polystyrene core-shell emulsion polymerization

The morphology of polybutylacrylate–polystyrene (PBA–PS) core-shell latex particles prepared by seeded emulsion polymerization was investigated as a function of the addition method of styrene (St). The thin layer chromatography/flame ionization detector (TLC–FID) technique was used to characterize the morphology of the core-shell latexes. It was found that grafting PS to the PBA core occurs during seeded emulsion polymerization. The percentage of grafting depended on the method of addition of St, being greatest for the batch reaction, less for the preswollen batch reaction, and least for the semibatch reaction. Upon aging the PBA core-polymer migrated out of the latex particles with a low degree of grafting to form dumbellshaped particles, whereas the PBA–PS core-shell particles with a high degree of grafting remained spherical because of the emulsifying ability of graft copolymer.     

Core-shell emulsion copolymerization of styrene and acrylonitrile on polystyrene seed particles

Seeded emulsion copolymerization of an azeotropic composition of styrene (St) and an acrylinitrile (AN) comonomer mixture in polystyrene (PS) seed at different polymerization temperature of 55–75°C were investigated. The kinetic data showed a transition temperature at 65°C, above which the activation energy of polymerization is low, 6.1 Kcal/mol, compared with 9.8 Kcal/mol below it. The particle-size results and thin layer chromatographic (TLC) data showed two types of particle of different composition and morphology in the final latex system: a smaller size of (St–AN) copolymer and a larger size of core-PS and (St–AN) copolymer shell, with a zone of PS grafted (St–AN) copolymer in between. Various polymerization parameters, that is emulsifier concentration, type of seed particle and its size, and monomer/polymer ratio, were studied and their effects on particle size and particle morphology were examined. The percent of grafted core-PS was 10% below a polymerization temperature of 65°C and 40% above that temperature. By adjusting the size and number of the seed particles, monomer-polymer ratio, and emulsifier concentration conditions were established in which a final copolymer latex with “perfect” core-shell morphology was achieved.     

Effective encapsulation of Sudan black B with polystyrene using miniemulsion polymerization

In this study, polystyrene (PS)/Sudan black B (SDB) latex particles were prepared using a miniemulsion polymerization technique in the presence of methyl isobutyl ketone (MIBK). Effects of the weight ratio of MIBK/styrene (St) and the SDB load on the morphology of latex particles and encapsulation efficiency were studied. It was found that the encapsulation efficiency of SDB with PS increased as the weight ratio of MIBK/St rose. The PS/SDB latex particles have a perfect core-shell structure and as high as more than 90% of encapsulation efficiency at 1:1 of MIBK/St. UV irradiation experiments and dynamic light scattering tests indicated that the obtained PS/SDB latexes exhibited excellent photostability and storage stability.