无规甲基化β-环糊精对甲基丙烯酸甲酯无皂乳液聚合影响的研究

采用溶液法制备了无规甲基化β-环糊精(RAMEB)/甲基丙烯酸甲酯(MMA)包合物。利用紫外-可见光谱、热重-差热分析等检测手段研究了RAMEB与MMA的包合作用。摩尔比法表明RAMEB与MMA可以形成化学计量比为1:1的包合物。TG -DSC分析表明RAMEB能与MMA形成较为稳定的包合物,从而使MMA的热稳定性大大提高。以MMA为单体,过硫酸钾为引发剂。研究了RAMEB对无皂乳液聚合反应的影响。结果表明,当RAMEB的加入量为0.5g时,体系在75℃反应30min时单体转化率达到89.21%,比同一时间下没有加入RAMEB的空白样的单体转化率提高了30.6%。当RAMEB的加入量为1g时,聚合反应速率比空白样低,单体的最终转化率与空白样差不多。同时,RAMEB的引入可以使得PMMA微球粒径变大,随着RAMEB加入量的增加,聚合物微球的大小越来越均匀。     

AC对St或MMA为壳层单体种子乳液聚合的影响

在种子乳液聚合中加入发泡剂偶氮二甲酰胺(AC),制备了可发气核壳结构复合微球。探讨了AC用量对以聚苯乙烯(PSt)微凝胶为种子,St或甲基丙烯酸甲酯(MMA)为壳层单体的2种体系稳定性及转化率和反应速率的影响。结果表明,以MMA为壳层单体的聚合体系是较理想体系。当AC用量从1g增加到8g时,以St为壳层单体体系的最终转化率从96．2％下降到74．2％,以MMA为壳层单体体系的最终转化率基本不变,保持在96％左右。但AC的加入使以MMA为壳层单体体系的反应速度最大值的出现时间推后了10min,且其值仅为未加入AC体系的1／2左右。     

MMA-CR体系中单体残留量的影响因素分析

采用顶空进样法对甲基丙烯酸甲酯(MMA)改性CR体系中的MMA单体残留量进行测定。试验结果表明,当反应条件为:乳液聚合反应温度70℃,MMA单体加入量6.5 g,引发剂用量0.13 g,乳化剂用量0.39 g时,单体残留量最小。     

无皂乳液聚合制备亚微米级单分散聚苯乙烯微球

采用无皂乳液聚合法制备了具有单分散性的亚微米级聚苯乙烯微球,考察了聚合体系pH值、单体及引发剂用量对聚合转化率、微球粒径及其分布的影响。结果表明,采用NaOH和NaHCO,复合溶液调节聚合体系pH值是控制聚合动力学、微球粒径及单分散性的有效手段,当其质量比为1：1时效果较好。随碱性复合溶液加入量的增加,最终转化率下降,微球粒径则由于复合溶液同时起到电解质的作用而存在极大值。随过硫酸钾(KPS)质量分数的增加,反应前期聚合转化率增大,但其用量过大,会导致体系pH值偏低,KPS过早消耗完毕,故反应后期最终转化率偏低;其用量过低,会影响粒径的单分散性。当KPS质量分数为单体的2％～3％时,聚合体系稳定性增加并改善了微球的单分散性,粒径趋小。单体用量的变化对聚合速率影响不大,随单体质量分数的提高,微球最终粒径增大,当单体质量分数过高,会影响微球的单分散性乃至体系失稳,一般以不超过10％为宜。     

悬浮聚合法制备PGMA-MMA-EGDMA共聚物交联微球

以甲基丙烯酸缩水甘油酯(GMA)为主单体、甲基丙烯酸甲酯(MMA)为共单体、乙二醇二甲基丙烯酸酯(EGDMA)为交联剂、聚乙烯醇(PVA)为分散剂,采用悬浮聚合法制备了三元共聚交联微球GMA-MMA-EGDMA,采用FT-IR和SEM对其化学结构和微球进行了表征,考察了分散剂用量、搅拌速度、油/水相比、交联剂用量、NaCl用量对交联微球的成球性能及粒度的影响规律. 结果表明,分散剂用量、搅拌速度与油/水相比是影响交联微球制备的主要因素,当分散剂用量<1%、搅拌速度<250 r/min、油/水相比>1:4(j)时,共聚合体系中均不能成球. 在水相中加入电解质NaCl有助于成球,交联微球的粒径随NaCl用量增大而减小. 控制悬浮聚合的反应条件可以制备出球形度好、粒径在100~400 mm范围内可控的交联微球GMA-MMA-EGDMA.     

无皂乳液聚合法制备PMMA/GMA/DVB复合微球及其表征

用无皂乳液聚合方法制备了PMMA/GMA/DVB复合微球,用重量法对其转化率进行了测试,结果表明聚合反应的转化率较高,都超过了90%.用盐酸-丙酮法对微球表面环氧基团的量进行表征.环氧单体加入时间的不同对微球表面环氧基团的量影响不大.随着环氧单体量的增多,环氧微球表面的官能团的量增多.随着交联剂DVB量的增加,环氧微球...     

水溶液聚合高分子聚丙烯酰胺的研究

采用复合氧化还原引发体系,以丙烯酰胺(AM)为单体水溶液自由基共聚合,合成了高相对分子质量的聚丙烯酰胺。研究了pH值等因素对聚丙烯酰胺相对分子质量的影响,并确定了最佳的反应条件:聚合温度55℃,单体质量分数7.5%,pH值为8,引发剂为C(过硫酸铵量)=12×10-4mol/L、C(亚硫酸氢钠量)=9.6×10-4mol/L的复合体系,聚合时间为3h,此条件下可获得相对分子质量高达3.05×106的聚丙烯酰胺产物。     

甲基丙烯酸甲酯-丙烯酸共聚物磁性微球的制备及其应用

采用悬浮聚合法制备了甲基丙烯酸甲酯-丙烯酸共聚物(MMA-AA)磁性微球,讨论了单体/水(质量比)、反应温度及反应时间的影响,研究了MMA-AA磁性微球的形态、平均粒径分布及表面官能团状况,将活化后的MMA-AA磁性微球与抗菌药物环丙沙星结合,并用示差脉冲伏安法进行了检测。结果表明,在单体/水为5·0/100、90℃下反应5h可制得具有单分散性的MMA-AA磁性微球;与环丙沙星结合后的MMA-AA磁性微球在-0·365V处有一还原峰,在浓度为6·26×10~(-9)~6·26×10~(-8)mol/L时,其峰电流与环丙沙星浓度具有线性关系,检测下限达到3·20×10~(-9)mol/L。     

浅谈我公司对PVC树脂老化白度的研究

介绍了齐化化工有限责任公司对提高PVC树脂热老化白度的研究。采取的措施 :(1)单体中含铁量控制 2× 10 -6以下 ;(2 )在生产高型号PVC树脂时 ,加入可消耗高能自由基的链转移剂 ;(3)聚合转化率控制在 80 %左右时出料 ;(4 )加入 0 .0 2 %以下的C7-9Zn。改进后使PVC树脂的白度控制在 85 %、粘数为 85mL/g。     

[Ru(CN)_6]~(3-)在溴碘化银T-颗粒乳剂中的掺杂

研究了K4犤Ru(CN)6犦掺杂剂对溴碘化银T-颗粒乳剂感光性能的影响,结果表明掺杂剂的掺杂量以及掺杂位置对乳剂的感光性能都有影响。当K4犤Ru(CN)6犦的掺杂量为3.1×10-8～3.1×10-9mol/g乳剂之间时,掺杂剂掺杂在乳剂的任意位置,乳剂感光度都有提高,表明K4犤Ru(CN)6犦是浅电子陷阱掺杂剂。掺杂位置接近表面或接近内核时效果相对较好,最佳的掺杂量为3.1×10-8mol/g乳剂。当掺杂剂的掺杂量小于3.1×10-10mol/g乳剂,且掺杂位置接近富碘区时,乳剂的感光度反而下降。     

Emulsion polymerization of methyl methacrylate in the presence of burnt mazote boiler deposit

The emulsion polymerization of methyl methacrylate (MMA) using different initiators was carried out in the absence and presence of burnt mazote boiler deposit (BMBD). When sodium persulfate or potassium persulfate was used, the initial rate of polymerization was found to decrease with increase of the burnt mazote boiler deposit concentration but to increase when sodium bisulfite was used as initiator. The initial rate of polymerization was found to be higher in nitrogen atmosphere than in air. The apparent activation energy (E_a) was found to be 12.4 × 10⁴ J/mol and 16.3 × 10⁴J/mol in the absence and presence of burnt mazote boiler deposit when potassium persulfate was used as initiator and 5.9 × 10⁴ J/mol and 5.1 × 10⁴ J/mol when sodium bisulfite was used as initiator, respectively. The mean average molecular weights for PMMA were found to increase with increase of the burnt mazote boiler deposit when sodium bisulfite was used as initiator.     

Poly(methyl methacrylate) nanoparticles prepared through microwave emulsion polymerization

The emulsifier‐free emulsion polymerization of methyl methacrylate (MMA) was conducted with microwave irradiation. Superfine and monodisperse poly(methyl methacrylate) (PMMA) microspheres were obtained. Microwave irradiation notably promoted the polymerization reaction. This phenomenon was ascribed to the acceleration of the initiator [potassium persulfate (KPS)] decomposition by microwave irradiation. The experimental results revealed that the apparent activation energy of KPS decomposition decreased from 128.3 to 106.0 kJ/mol with microwave irradiation. The average particle size of the prepared PMMA latex was mainly controlled with the MMA concentration; it increased linearly from 103 to 215 nm when the MMA concentration increased from 0 to 0.3 mol/L and then remained almost constant at MMA concentrations of 0.3–1.0 mol/L. The KPS concentration had no effect on the average particle size, but the particle size dispersity was significantly reduced by a high KPS concentration. With a mixed polymerization phase (water/acetone = 1:3 v/v) or a redox initiation system, PMMA nanoparticles were obtained with an average particle size of 45 or 67 nm, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2815–2820, 2004     

苯乙烯-甲基丙烯酸甲酯悬浮-乳液耦合聚合动力学

采用苯乙烯(St)悬浮聚合过程滴加甲基丙烯酸甲酯(MMA)乳液聚合组分,进行悬浮-乳液耦合聚合(SECP), 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¹H NMR分析方法,讨论了SECP动力学特征.St的SECP聚合速率和转化率与悬浮聚合一致;MMA聚合速率决定于乳胶粒子聚合速度和凝并在悬浮粒子表面的速度,聚合速率比常规乳液聚合速率低.由于凝并在悬浮粒子表面的PMMA乳胶粒子不再有乳液聚合特征,MMA在SECP中转化率低于同条件常规乳液聚合.分别得到乳化剂和引发剂浓度与SECP和普通乳液聚合恒速段聚合速率的关系.     

Particle features of a poly(methyl methacrylate) resin prepared by a new emulsion polymerization process

A new emulsion polymerization process, in which water acted as the dispersed phase and a mixture of methyl methacrylate (MMA) and cyclohexane acted as the continuous phase, was applied to the preparation of a poly(methyl methacrylate) (PMMA) resin. The primary (latex) particles were formed in the early stage of polymerization and coagulated as the polymerization conversion increased. Scanning electron micrographs showed that the final PMMA particles were porous and composed of loosely aggregated primary particles. The porosity characterized by cold di(2‐ethylhexyl) phthalate absorption increased as the water/oil and cyclohexane/MMA mass ratios increased. The PMMA primary particles were smaller than the primary particles in the PMMA resin prepared by suspension polymerization in the presence of cyclohexane. Because of the phase composition of the reaction system, the solubility of PMMA in a mixture of cyclohexane and MMA, and the particle morphology of PMMA, a particle formation mechanism, including the formation, growth, and coagulation of primary particles in dispersed water droplets, was proposed. The primary particles formed mainly through a homogeneous nucleation mechanism and increased in size as MMA diffused from the oil phase to the water phase to the primary particles. The coagulation of the primary particles occurred because of the lower colloidal stability and the space limitations of the primary particles. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1905–1911, 2004     

无规甲基化β-环糊精与苯乙烯包结物的制备和表征

在水溶液中制备了无规甲基化β-环糊精(RAMEB)/苯乙烯包结物。利用热重-差热分析、紫外-可见光谱及核磁共振波谱等检测手段研究了无规甲基化β-环糊精与苯乙烯的包合作用,对包结物的结构、性能进行了表征和分析。运用紫外-可见光谱测试溶液吸光度的变化,摩尔比法表明无规甲基化β-环糊精与苯乙烯包结物的摩尔比为1∶1。Benesi-Hildebrand方程进一步确定了包结反应的包结比以及计算出该温度下的平衡常数,表明无规甲基化β-环糊精与苯乙烯形成了摩尔比为1∶1的包结物。     

Controlled radical polymerization catalyzed by CuCl/BDE complex in water medium. II. Polymerization of methyl methacrylate and formation of PMMA with bimodal molecular weight distribution

The emulsion polymerization of MMA was explored for the BDE/CuCl coordinated catalyst. The M_n of PMMA linearly increased both with increasing the monomer conversion and the proceeding polymerization time, which means that the MMA polymerized in “living”/controlled characters with zero order kinetics under BDE/CuCl‐catalyzed emulsion conditions. The apparent polymerization rate constants of MMA were k = 0.765 mol/min, k = 0.760 mol/min at 80°C, while k = 0.228 mol/min at 50°C, respectively. Slight differences of polymerization results were obtained when emulsifier lauryl phosphate (ADP) and Polyoxyethylene nonyl phenyl ether (OP‐10) were adapted in the polymerization. Based on the “coordinated radical cage” mechanism proposed particularly to the BDE/CuCl catalyzed polymerization, reversible equilibrium between common free radical and the coordinated “living” species should exist in this system. Increasing the amount of catalyst must affect the fast equilibrium between those two species, thus, also affecting the relative content in the emulsion circumstance. Therefore, PMMA, with bimodal molecular weight distribution, was achieved through this approach. The formation of PMMA with bimodal distribution was affected by concentration of catalyst and polymerization temperature. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3076–3081, 2002; DOI 10.1002/app.2336     

Mechanistic study of the formation of amphiphilic core-shell particles by grafting methyl methacrylate from polyethylenimine through emulsion polymerization

The mechanism for the formation of amphiphilic core-shell particles in water is elucidated via a kinetic study of semi-batch polymerization of methyl methacrylate (MMA) grafted from polyethylenimine (PEI) initiated with tert-butyl hydroperoxide in an emulsion polymerization. The monomer conversion, the polymerization kinetics, the particle size, the particle number density, the poly(methyl methacrylate) (PMMA) core diameter, the percentage of unbound PEI, and the grafting efficiency of PMMA were determined at various times during the polymerization. The particle number density and the percentage of unbound PEI were almost independent of the controllable variables. The particle sizes and the core diameters increased with each consecutive batch of monomer addition, while the grafting efficiency of PMMA decreased. These data supported the hypothesis that the PEI-g-PMMA graft copolymers were formed early in the polymerization and later self-assembled to a new phase, micellar microdomains. These microdomains act as loci for subsequent MMA polymerization as the monomer is fed into the reaction, without subsequent formation of new particles. The size of the resulting highly uniform core-shell particles (99-147 nm) can be controlled by choosing the amount of monomer charged. Thus, this polymerization method is viable for a large scale production of core-shell particles with high solids content.     

Effects of reaction conditions on poly(methyl methacrylate) polymerized by living radical polymerization with iniferter

Living radical polymerization of methyl methacrylate (MMA) through the use of benzyl diethyl dithiocarbamate (BDC) was studied. The aim was to investigate the role of the concentration, BDC‐to‐MMA mol ratio, and reaction time upon the molecular weight, polydispersity, and conversion of the product. It was found that the molecular weight and the conversion increase with increase of the concentration at the expense of low polydispersity. The reaction time also played a significant role, especially at a relatively long reaction time where molecular weight, polydispersity, and conversion increased with increasing reaction time. In terms of the mol ratio effect, it was found that there was a critical mol ratio for maximum conversion. The results indicate that the kinetics of polymerization of MMA through the use of a BDC inifeter is different from that in the presence of a conventional initiator. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 938–944, 2000     

Effect of graft chain length of the stabilizer on dispersion polymerization of methyl methacrylate in petrol

To carry out dispersion polymerization of methyl methacrylate (MMA) in petrol, we have used a poly(MMA) grafted-poly(12-hydroxystearic acid) copolymer as the stabilizer. This special copolymer was prepared as a solution in a mixture of ethyl acetate and butyl acetate solvents. We investigated the effect of graft chain length of the stabilizer on the dispersion polymerization in petrol. We synthesized the stabilizer copolymer with n = 1–4 and determined the rate and the molecular weight of the PMMA formed. There is no dispersion polymerization for n = 1. However, for any other n, for a given stabilizer concentration, as the chain length of the graft is increased, the molecular weight as well as the rate of PMMA formation increases. As opposed to this for a given graft length as the concentration of the stabilizer increases, the molecular weight of PMMA first rises, but for a larger concentration, it begins to fall after undergoing a maximum. In this work, we modeled the heterogeneity of the reaction mass and proposed a mathematical model for dispersion polymerization of MMA in petrol. The computer results are found to conform to the experimentally observed molecular weight of the PMMA. © 1993 John Wiley & Sons, Inc.     

Phase behavior and properties of poly(methyl methacrylate)/poly(vinyl acetate) blends prepared via in situ polymerization

Polymer blends composed of poly(methyl methacrylate) (PMMA) and poly(vinyl acetate) (PVAc) were prepared via radical-initiated polymerization of methyl methacrylate (MMA) in the presence of PVAc. Differential scanning calorimetry and dynamic mechanical analysis were employed to investigate the miscibility and phase behavior of the blends. The PMMA/PVAc blends of in situ polymerization were found to be phase separated and exhibited a two-phase structure, although some chain transferring reaction between the components occurred. The phase separation resulted from the solvent effect of MMA during the in situ polymerization, which was confirmed by the investigation of phase behavior based on solution cast blending. Solubility analysis of the polymerized blends indicated that some chain transferring reaction between the components occurred during the polymerization. An abrupt increase in gel content from 21.2 to 72.4 wt % was observed when the inclusion of PVAc increased from 30 to 40 wt %, and the gel component consisted of the component polymers as shown by infrared spectroscopy studies. The thermogravimetric analysis study indicated that the inclusion of a small amount of PVAc gives rise to a marked stabilization effect on the thermal stability. The PMMA/PVAc blends exhibited increased notched impact properties with the inclusion of 5 wt % PVAc. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 675–684, 1998