PU-St超浓乳液聚合动力学及聚合物性质的研究

采用一步法制备聚氨酯预聚体 ( PU)苯乙烯 ( St)超浓乳液 ,探讨了稳定的超浓乳液的 NCO/OH和 St/PU最佳比例范围。研究了乳化剂和引发剂浓度对超浓乳液聚合的稳定性及聚合动力学的影响 ,并制得了用 PU改性的聚苯乙烯 ( PS)粉状树脂。测定了乳胶粒子大小、粒径分布、分子量和聚合物膜的动态力学性质。发现乳胶粒子大小及其单分散性随聚合转化率的增加而增加 ;与本体聚合比较 ,聚合物的分子量有明显增大 ;PU- PS复合聚合物具有优良性能。     

非离子型可聚合聚氨酯/苯乙烯的超浓乳液聚合

研究了以非离子型可聚合聚氨酯(PUAG)和苯乙烯(St)为混合单体的超浓乳液聚合, 并且考察了n(NCO)/n(OH)摩尔比、复合乳化剂体系质量浓度[E]、不同乳化剂的种类、引发剂质量浓度[I]、单体体积分数(或分散相体积分数, 也称内相比Φ)、聚合温度等因素对聚合稳定性、动力学的影响. 同时结合光相关光谱(PCS)测定了聚合物乳胶粒子大小和粒径分布, 用透射电子显微镜(TEM)观察了粒子形态, 结果表明: 当n(NCO)/n(OH)＝2∶1, T＝328 K, Φ＝80.39%, [I]＝0.8% g/g (PUAG-St), [E]＝0.22 g/mL H₂O, m(MS-1)/m(CA)＝2∶1, PVA＝0.01 g/mL H₂O时, 超浓乳液不仅有较好的聚合稳定性和较快的聚合速率, 而且粒径小分布均匀. 同时, 在此条件下的表观动力学表达式和表观活化能分别确定为R_p＝k[I]^0.50[E]^0.73[M]^0.54和 E_a＝29.7 kJ/mol. 热失重分析(TGA)进一步表明: 调节PUAG的含量可以达到对聚苯乙烯的改性, 提高聚苯乙烯的热稳定性.     

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.     

氧化还原低温引发MMA/BA超浓乳液薄层共聚合的研究

以甲基丙烯酸甲酯-丙烯酸丁酯(MMA-BA)作为混合单体、以乳化剂十二烷基硫酸钠(SDS)和共乳化剂十六烷醇(CA)作为复合乳化剂体系、聚乙烯醇(PVA)为液膜增强剂,制备了稳定的超浓乳液.以过氧化二苯甲酰(BPO)和N,N′-二甲基苯胺(DMA)为氧化还原引发体系,用一种新的超浓乳液薄层技术,在较低温度下引发共聚合.探讨了液膜增强剂种类和聚合环境对聚合稳定性影响;研究了薄层厚度,薄层面积,聚合温度和加热方式对体系(包括单体和水)挥发性和转化率的影响.比较了薄层和试管聚合的速率.用透射电子显微镜观察了水浴与烘箱加热方式下聚合物乳胶粒的形态,得到了在水浴中反应后的聚合物粒子平均粒径和分散度都减小的结果.     

氧化-还原低温引发甲基丙烯酸甲酯/丙烯酸丁酯超浓乳液聚合研究

以乳化剂十二烷基硫酸钠 (SDS)和共乳化剂十六烷醇 (HD)作为复合乳化体系 ,过氧化二苯甲酰(BPO)和N ,N 二甲基苯胺 (DMA)作为氧化还原引发体系 ,甲基丙烯酸甲酯 丙烯酸丁酯 (MMA BA)作为混合单体 ,制备了分散相占 83 %以上的稳定的超浓乳液 ,然后在低温下引发聚合 .探讨了引发剂浓度、氧化剂与还原剂的摩尔比、乳化剂的浓度、液膜增强剂的种类、聚合温度等因素对聚合稳定性和聚合速率的影响 ,测定并计算得到了聚合速率的公式 ;用激光散射粒度分布仪测定了聚合物乳胶粒子的大小及粒径分布 ,用透射电子显微镜观察了聚合物乳胶粒的形态 ,讨论了乳化剂浓度、聚合温度等对乳胶粒形态、大小的影响     

氧化—还原低温引发苯乙烯／丙烯酸丁酯细乳液聚合粒度分 …

用氧化还原引发剂（ＮＨ４）２Ｓ２Ｏ８／ＮaＨＳＯ３研究了苯乙烯（Ｓt）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     

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.     

复合微乳液聚合制备P(MMA-UA)纳米乳胶粒子的研究

将聚氨酯预聚体可聚合乳化剂 (APUA)和甲基丙烯酸甲酯 (MMA)的复合微乳液体系 ,分别用水溶性过硫酸钾 (K2 S2 O8)和油溶性偶氮二异丁腈 (AIBN)作引发剂 ,进行微乳液聚合研究 ,制备了P(MMA UA)复合纳米乳胶粒子 .研究了APUA用量、聚合温度对聚合动力学的影响 ;用透射电子显微镜 (TEM)观察了不同乳化剂浓度及引发剂体系对胶粒形态、大小及分布的影响 .结果表明 ,用可聚合乳化剂APUA可制得稳定性很好的P(MMA UA)纳米级核 壳型乳胶粒子 ,乳胶粒径在 5 0nm左右 .随着乳化剂用量增加 ,粒子变小 ;不同类型的引发剂对胶乳的性质有较大影响 ,以APUA为乳化剂 ,K2 S2 O8为引发剂 ,在聚合反应过程中或在聚合反应后的放置中 ,会出现P(MMA UA)的纳米水凝胶 (Nanogel)现象 .     

UV光引发的丙烯酰胺反相乳液聚合

报道了不透明丙烯酰胺反相乳液体系的UV光引发聚合新方法 .使用普通中压汞灯并辅以适当搅拌 ,UV光引发丙烯酰胺 水 煤油 Span80 +OP 10反相乳液聚合可在 2 0min左右完成 ,所得聚合物分子量达千万 ;聚合过程中不存在恒速期 ,扫描电镜未观察到聚合前后乳胶粒径有数量级的变化 ,表明聚合反应以单体液滴成核为主 .此外 ,考察了光引发剂类型及浓度、单体浓度、乳化剂用量、反应温度等对聚合反应的影响 ,结果表明不同光引发剂的引发活性为Irgacure 2 95 9>(ITX +EDAB) >BDK ,引发剂浓度增加 ,反应速度先增加而后降低 ,存在一最大值 ;单体浓度增加 ,反应速度加快 ,聚合物分子量提高 ;乳化剂用量增加 ,反应速度加快而分子量变化不明显 ;聚合表观活化能为 13 34kJ mol.     

电荷转移引发聚合——酚噻嗪引发丙烯腈光聚合研究

本文研究了酚噻嗪(PTZ)引发丙烯腈(AN)的光聚合。测定了聚合速率R_p=K[AN]^1.47[PTZ]^0.41及活化能E_α=7.1千卡/摩尔。从PTZ与AN在光照下形成激基复合物的机制讨论了引发聚合机理。     

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     

Kinetic and particle size studies of emulsion polymerization of methyl methacrylate and styrene with using polyamidoamine dendrimer as seed

The emulsion polymerization of methyl methacrylate (MMA) and styrene (St) were investigated with using polyamidoamine (PAMAM) dendrimer as seed, potassium persulfate as initiator and sodium dodecyl sulfate as emulsifier. The effects of 4.0GPAMAM dendrimer concentration, initiator concentration, emulsifier concentration, monomer concentration, and polymerization temperature on the monomer conversion and polymerization rate were investigated. At the same time, the influence of the generation of PAMAM dendrimer on latex particle size was studied also. The results showed that the monomer conversion and polymerization rate increased with increasing initiator concentration, emulsifier concentration, monomer concentration, and polymerization temperature. But polymerization rate increased firstly with an increase in the 4.0GPAMAM dendrimer from 0.03 g to 0.09 g and then decreased with further increase to 0.12 g. When the concentration of 4.0GPAMAM dendrimer less than 1.449 × 10^?4 mol/L, the kinetic equation can be expressed by Rp∝[4.0GPAMAM]^0.772[SDS]^0.562[KPS]^0.589[M]^0.697, and the activation energy (Ea) of emulsion polymerization is 62.56kJ/mol. In additional, the copolymer latex particle size decreased and possessed monodispersity with increasing the generation of PAMAM dendrimer. According to FT-IR spectrum analysis, PAMAM dendrimer is successfully incorporated into the poly(PAMAM-St–MMA) latex particles.     

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.     

表面活性单体存在下的MMA/BA乳液共聚合(Ⅱ)聚合动力学及机理

研究了表面活性单体[磺化-十二醇-烯丙基甘油-丁二酸酯钠盐(ZC-L)]的用量对MMA/BA/ZC-L乳液聚合速率和粒径的影响,用CoulterLS230型激光粒径分析仪测定聚合过程中乳液的粒径和粒径分布变化,并与MMA/BA无皂乳液聚合及十二烷基苯磺酸钠存在下的MMA/BA乳液聚合作了比较.[ZC-L]CMC时,成核机理包括均相成核和胶束成核机理,生成的粒子因吸收体系中的表面活性单体而稳定存在.     

表面活性单体存在下的MMA／BA乳液共聚合（Ⅱ）：聚合动力？…

研究了表面活性单体「磺化－十二醇－烯丙基甘油－丁二酸酯钠盐（ＺＣ－Ｌ）」的用量对ＭＭＡ／ＢＡ／ＺＣ－Ｌ乳液聚合速率和粒径的影响,用Ｃｏｒｌｔｉｒ ＬＳ２３０型激光粒径分析仪测定聚合过程中乳液的粒径和粒径分布变化,并与ＭＭＡ／ＢＡ无皂乳液聚合及十二烷基苯磺酸钠存在下的ＭＭＡ／ＢＡ乳液聚合作了比较。「ＺＣ－Ｌ」〈ＣＭＣ时,成核机理为均相成核机理,乳胶粒需依靠粒子间的凝聚来提高表面电荷密度而稳定;「ＺＣ     

Pickering emulsion polymerization of graphene oxide-stabilized styrene

Polystyrene (PS) particles were prepared via Pickering emulsion polymerization using graphene oxide (GO) as the stabilizer. The results show that pH is an important factor in the stability of Pickering emulsions. The effects of two different phase initiators, the water phase initiator potassium persulfate and the oil phase initiator azobisisobutyronitrile, on the morphology of PS particles in Pickering emulsion polymerization had been investigated in detail. Wrinkled particles were prepared using the water phase initiator, and spherical particles were prepared using the oil phase initiator. In addition, hexadecane was used as the auxiliary stabilizer in the polymerization, which narrowed the diameter distribution of the PS spheres, and the hollow PS spheres were fabricated. The size of the GO particles also influenced the final morphology of the particles. Nano-sized polymer particles were grafted onto the surface of micro-sized GO. Small GO particles were suitable for Pickering emulsion polymerization to prepare the composite particles. The thermogravimetric analysis of the prepared particles confirmed that they were PS/GO composite particles, which could have a wide range of potential applications, such as in catalysts, sensors, environmental remediation, and energy storage.     

Synthesis of Latex Particles with Surface Functional Groups and Their Applications for the Fabrication of Porous Materials

In this study, monodisperse latex particles with specific surface functional groups were synthesized by emulsifier-free emulsion polymerization. Amidine or carboxylated polystyrene nanospheres with narrow size distribution were prepared by emulsion polymerization using AIBA (α,α′-zodiisobutyramidine dihydrochloride) as amine-containing initiator or acrylic acid as carboxyl-containing comonomer, respectively. Factors affecting the particle size and distribution were systemically studied by changing the amount of initiator or monomer, the polymerization temperature, and the stirring speed of emulsion polymerization reactor. Monodisperse polymethylmethacrylate beads were also synthesized by soapless emulsion polymerization using methacrylic acid or aminoethylmethacrylate hydrogen hydrochloride as comonomer for the surface functionalization of the particles. As applications of the latex beads, the polymeric particles were adopted as templating materials for the fabrication of macroporous titania film and meso-macroporous silica particles by colloidal templating method.     

Poly(2-acetoxyethyl methacrylate)/polystyrene latex interpenetrating polymer networks with well-defined phase-separated structure

A series of poly(2-acetoxyethyl methacrylate)/polystyrene(PAEMA/PS) latex interpenetrating polymer networks(LIPNs) were prepared by seeded soap-free emulsion polymerization of styrene on the crosslinked PAEMA seed particles using an oil-soluble initiator.These PAEMA/PS LIPNs showed a well-defined phase-separated structure with PS phase dispersing in continuous PAEMA phase.The domain size of PS phase was found to depend on the crosslinking degree of PAEMA seed particles and the amount of second-stage styrene monomer.     

Synthesis and morphology of Fe3O4/polystyrene/poly(isopropylacrylamide‐co‐methyl acrylate acid) magnetic composite latex – 2,2′‐azobis (2‐methylpropionamidine) dihydrochloride as initiator

In this work, Fe₃O₄/polystyrene/poly(N‐isopropylacryl amide‐co‐methylacrylate acid) (Fe₃O₄/PS/P(NIPAAM‐co‐MAA)) magnetic composite latex was synthesized by the method of two stage emulsion polymerization. In this reaction system, 2,2′‐azobis(2‐methyl propionamidine) dihydrochloride (AIBA) was used as initiator to initiate the first stage reaction and second stage reaction. The Fe₃O₄ particles were prepared by a traditional coprecipitation method. Fe₃O₄ particles were surface treated by either PAA oligomer or lauric acid to form the stable ferrofluid. The first stage for the synthesis of magnetic composite latex was to synthesize PS in the presence of ferrofluid by soapless emulsion polymerization to form the Fe₃O₄/PS composite latex particles. Following the first stage of reaction, the second stage of polymerization was carried out by the method of soapless emulsion polymerization with NIPAAM and MAA as monomers and Fe₃O₄/PS latex as seeds. The magnetic composite particles, Fe₃O₄/PS/P(NIPAAM‐co‐MAA), were thus obtained. The mechanism of the first stage reaction and second stage reaction were investigated. Moreover, the effects of PAA and lauric acid on the reaction kinetics, morphology, and particle size distribution were studied. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3912–3921, 2007     

Synthesis of polystyrene/poly[2-(dimethylamino)ethyl methacrylate-stat-ethylene glycol dimethacrylate] core-shell latex particles by seeded emulsion polymerization and their application as stimulus-responsive particulate emulsifiers for oil-in-water emulsions

Surfactant-stabilized polystyrene (PS) latex particles with a mean hydrodynamic diameter of 155 nm were prepared by aqueous emulsion polymerization using 2,2'-azobis(2-amidinopropane) hydrochloride as a cationic radical initiator. Seeded aqueous emulsion copolymerizations of 2-(dimethylamino)ethyl methacrylate (DMA) and ethylene glycol dimethacrylate (EGDMA) were conducted in the presence of these PS particles to produce two batches of colloidally stable core-shell latex particles, in which the shell comprised a cross-linked P(DMA-stat-EGDMA) overlayer. Both the PS and PS/P(DMA-stat-EGDMA) latexes were characterized in terms of their particle size, morphology, and composition using dynamic light scattering, electron microscopy, and FT-IR spectroscopy, respectively. Using the PS/P(DMA-stat-EGDMA) latex particles as a pH-responsive particulate ('Pickering'-type) emulsifier, polydisperse n-dodecane-in-water emulsions were prepared at pH 8 that could be partially broken (demulsified) on lowering the solution pH to 3. These emulsions were characterized in terms of their emulsion type, mean droplet diameter, and morphology using electrical conductivity and Mastersizer measurements, optical microscopy, and scanning electron microscopy (using critical point drying for sample preparation).