影响苯乙烯丙烯腈在聚丁二烯乳胶粒上接枝共聚反应的因素

采用种子乳液聚合技术在聚丁二烯 ( PB)乳胶粒上接枝共聚苯乙烯 ( St)和丙烯腈 ( AN) ,合成了一系列 PB-g-SAN共聚物 ( ABS)。将这些共聚物用丙酮溶解并在超速离心机上将 PB-g-SAN和未接枝在 PB上的游离 SAN分离 ,计算出 SAN在 PB上的接枝率和接枝效率。通过改变共聚单体的组成和加料时间 ,研究了接枝率和接枝效率的变化。结果表明 SAN的接枝率随着 PB含量的增加而降低 ,在共聚单体中增加引发剂 ( CHP)和分子量调节剂 ( TD-DM)的含量 ,SAN在 PB上的接枝率和接枝效率表现出了下降的趋势 ,而共聚单体的配比 St/ AN和加料时间对接枝率和接枝效率的影响不大。     

核壳型复合聚合物乳液合成工艺研究

以乳化单体加料的种子聚合技术,合成了聚丙烯酸乙酯/聚苯乙烯核壳型复合聚合物乳液.确定了种子聚合过程中乳化剂补加量与聚合单体量之间的定量关系和合理的单体加料速率.该体系所得聚台物乳液的乳胶粒是“翻转型”的核壳结构.     

Preparation and characterization of imidazole‐functionalized microspheres

The preparation of imidazole‐functionalized latex microspheres by a two‐stage emulsion copolymerization process and their characterization are reported on. Emulsifier‐free emulsion copolymerization of styrene (St) and 1‐vinyl imidazole (VIMZ) exhibited bimodal particle size distributions caused by secondary homogeneous nucleation process. However, secondary nucleation can be avoided by using cetyltrimethylammonium bromide (CTAB) as a stabilizer at a concentration below its cmc (critical micelle concentration). This would result in the formation of monodisperse latex particles. The final particle size diameter depended on the concentration of CTAB as well as the amount of VIMZ. To control the amount of the functional imidazole groups on the latex particle surfaces, independent of the latex diameters, without secondary nucleation of particles, the seeded emulsion copolymerization of styrene and VIMZ was explored as a second‐stage polymerization at different concentrations and ratios of monomers in the presence of the previously prepared monodisperse poly(styrene‐co‐1‐vinyl imidazole) seed latex particles. The concentration of imidazole functional groups on the surface of the latex particles could also be varied through the rearrangement of hydrophilic imidazole groups by varying the second‐stage monomer addition process such as the utilization of monomer‐swollen seed particles or a shot addition of monomers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 120:5753–5762, 2006     

Grafting mechanism in SBR–St–MMA core–shell emulsion copolymerization

The graft copolymerization of styrene and methyl methacrylate on SBR latex particles in the core–shell emulsion process was conducted in a 600 mL glass stirred vessel with the BPO? Fe²⁺ redox initiator. The effects of the principal factors such as the polymerization temperature, monomer-to-polymer ratio, the frequency of monomer addition and conversion on the grafting degree, and the grafting efficiency were studied. The surface-controlled process model was proposed to describe the grafting mechanism. © 1994 John Wiley & Sons, Inc.     

Attapulgite@polymer particles with double‐layer polymer shell via soapless seeded emulsion polymerization

Attapulgite needle encapsulated with double‐layer polymer shell (ATP@DP) were prepared by the soapless seeded emulsion polymerization of the second monomer styrene in the dispersion of the attapulgite needle encapsulated with poly(methyl methacrylate) (ATP@PMMA), which was also conducted by the soapless seeded emulsion polymerization of the first monomer methyl methacrylate with the cetyltrimethylammonium bromide (CTAB) modified attapulgite needle (org‐ATP) as seeds. The different morphologies of ATP, ATP@PMMA particles, and ATP@DP particles were characterized by transmission electron microscopy, and the encapsulation mechanism was also discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Control of pore generation and pore size in nanoparticles of poly(styrene‐methyl methacrylate‐acrylic acid)

Seeded emulsion polymerization of styrene‐methyl methacrylate‐acrylic acid onto seed latexes of monodisperse particles of poly(styrene‐methyl methacrylate) was conducted with or without divinyl benzene as a crosslinking agent. Experiments revealed that almost no new particles were formed during the second stage of polymerization, and that the seeded latex particles obtained were almost monodisperse. An alkali‐acid treatment was then applied to the seeded latex particles swollen in 2‐butanone. Experimental results indicated that: (1) for uncrosslinked particles, an optimum volume expansion of >50% is reached for a ratio of the swelling agent, 2‐butanone, to polymer (methyl‐ethyl‐ketone/polymer by weight) between 2.0 and 2.9; the volume expansion is much lower outside the above range. (2) For crosslinked particles, the particle volume expansion follows the same pattern, but with smaller values. (3) pH plays an important role in pore generation and volume expansion. Pore generation is optimized by decreasing pH to a value as low as 1.5 during acid treatment, and by keeping pH in the optimum range between 11.98 and 12.20 during alkali treatment. Based on the above observations, a discussion regarding the mechanism of pore generation and particle expansion is provided. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 419–426, 1999     

Preparation of monodispersed hollow polymer particles by seeded emulsion polymerization under low emulsifier conditions

In a low emulsifier system, the MMA‐BA‐MAA copolymer emulsions were prepared as seed latices and the seeded emulsion polymerization of MMA‐MAA‐DVB was consequently carried out to prepare carboxylated core particles. The hydrophobic shell was then synthesized onto the core using styrene, acrylonitrile, and divinylbenzene as comonomers. The hollow latex particles were obtained by alkalization treatment of the core‐shell latex particles. The effects of the feeding rate of monomer mixture, contents of emulsifier SDBS and crosslinking agent DVB, and ratio of the monomers during the core stage and shell stage on the morphology and volume expansion of the latex particles were investigated. The results show that the monodispersed hollow latex particles with large size can be obtained when the feeding rate is 0.1 g/min, SDBS content is 0.15 and 0.2 wt % during the core stage and shell stage, respectively, DVB contents are 1% during the preparation of shell copolymers, and the monomer ratio of the core particle to shell layer is 1 : 8. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1505–1510, 2005     

乳液接枝聚合的反应控制对ABS树脂性能的影响

采用种子乳液聚合方法合成PB-g-SAN(ABS)接枝共聚物,与苯乙烯丙烯腈共聚物(SAN)熔融共混制备ABS树脂。主要研究了在聚丁二烯橡胶粒子(PB)上接枝苯乙烯(St)和丙烯腈(AN)单体制备ABS接枝共聚物过程中,单体的加料时间和预溶胀过程的控制对单体的接枝效果、ABS橡胶粒子的形态以及最终ABS树脂性能的影响。实验结果表明:与一次投料工艺相比,在接枝过程中连续进料方式有助于提高接枝效率,且单体连续加料时间适当缩短有助于提高ABS树脂的冲击强度;单体预溶胀过程会降低接枝效率,并且容易使St单体进入PB相形成内包容结构,接枝过程中保持预溶胀合适的单体量有助于提高ABS树脂的冲击强度。     

Polymer latex containing carboxylic acid functional groups. I. Synthesis of polymer latex from MMA and AA

The polymer latex of poly(MMA‐AA) was synthesized using two techniques: soapless seeded emulsion polymerization, and the soapless emulsion copolymerization technique. The reaction kinetics, morphology, composition, and size of latex particles, as well as the structure using thin‐layer chromatographic separation techniques, glass transition temperature (T_g), and molecular weight of polymer products, were studied under different experimental conditions. The reaction of the hydrophilic AA monomer took place in two places—on or in the latex particles, and in the water phase. Therefore, the polymer latex, whose size is very small and uniform, dispersed uniformly all over the PAA continuous phase. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3111–3120, 1999     

聚合型紫外线吸收剂的合成研究Ⅰ.含2-羟基-4-丙烯酸酯基二苯甲酮的丙烯酸酯类乳液聚合

通过“粒子设计”利用核壳乳液聚合技术以功能型紫外线吸收剂、苯乙烯、丙烯酸丁酯、甲基丙烯酸甲酯、丙烯酸乙酯为单体制备出核壳结构的聚合物乳胶粒。其中,功能型紫外线吸收剂2-羟基-4-丙烯酸酯基二苯甲酮由2,4-二羟基二苯甲酮和丙烯酰氯制备。通过紫外分光光度法测试,此乳胶粒的吸收度大于同浓度下的功能型单体及2,4-二羟基二苯甲酮。     

提高核壳ACR乳液接枝效率的新方法——引发剂型单体

提出了一种提高种子乳液聚合接枝效率的新方法。在种子乳液聚合阶段加入一种引发剂型单体,通过其引发聚合和参与聚合的双重功能,制备出了接枝效率较高的加工和抗冲击改性剂丙烯酸酯类(ACR)。讨论了引发剂型单体、引发剂型单体用量、交联剂用量及接枝单体用量对接枝聚合的接枝效率和接枝率的影响。     

ABS树脂的性能与形态结构设计 ⅠSAN在PB橡胶粒子上接枝率的控制及其对ABS树脂结构和性能的影响

采用种子乳液聚合技术在聚丁二烯乳胶粒上接枝共聚苯乙烯和丙烯腈 ,通过改变共聚单体和聚丁二烯的投料比合成了一系列PB g SAN共聚物 ,将这些共聚物与SAN树脂进行熔融共混制得了ABS树脂。研究了投料比对SAN在PB上的接枝率、SAN的分子量和ABS树脂的形态结构及性能的影响。结果发现 ,随着投料比的增加 ,SAN在PB上的接枝率及SAN的分子量提高 ,接枝率和SAN分子量共同作用影响着ABS树脂的冲击韧性和加工性能。形态结构研究结果表明 ,投料比不仅影响着橡胶粒子在SAN基体中的分散程度 ,而且影响着橡胶粒子的内部结构 ,随着投料比的增加 ,橡胶粒子在基体中的分散程度提高 ,其内部的包容结构增多并导致了橡胶粒子粒径的增大。     

Monodisperse‐porous poly(styrene‐co‐divinylbenzene) beads providing high column efficiency in reversed phase HPLC

A multistage polymerization protocol, the so‐called “modified seeded polymerization,” was developed for the production of monodisperse‐porous poly(styrene‐co‐divinylbenzene) providing high column efficiency as a packing material in reversed phase high performance liquid chromatography (RPLC). In the first stage of the multistage production, uniform polystyrene seed particles, produced by dispersion polymerization, were swollen by an organic agent (i.e., the diluent) and then by a monomer mixture containing styrene and divinylbenzene. The final porous particles were obtained in the monodisperse form by the polymerization of monomer mixture in the seed particles. By the use of a small size seed latex with low molecular weight and by the selection of the appropriate diluent, relatively small monodisperse‐porous particles with suitable pore structure could be achieved. In the reversed phase separation of alkylbenzenes, under isocratic conditions, theoretical plate numbers up to 40,000 plates/m were achieved by using 5.2 μm porous particles, obtained by a toluene‐dibutyl phthalate mixture as the diluent. No significant decrease in the resolution power was observed by the fourfold increase in the mobile phase flow rate. The column efficiency and the resolution observed with 5.2 μm monodisperse‐porous particles were significantly higher with respect to the currently available polymer based packing materials used in the reversed phase HPLC. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1430–1438, 2005     

伴有水解缩合反应的种子乳液聚合动力学(Ⅰ)模型

伴有水解缩合反应的自由基种子乳液聚合反应是制备有机-无机杂化乳胶粒的一种新方法,水解缩合反应和自由基聚合这两种反应在乳液体系中的动力学耦合过程决定了聚合产物的微结构和应用性质.通过单体的分配系数建立了单体在乳液体系中各相的分配模型,进而建立了考虑单体分配的自由基种子乳液共聚合的动力学模型.针对功能基团在乳液各相中水解缩合反应的特点,结合自由基种子乳液共聚合的动力学模型,建立了伴有水解缩合反应的自由基种子乳液聚合动力学模型.该模型反映了反应过程中的物质传递规律、非均相反应特点、自由基共聚合和水解缩合反应间的耦合关系.     

伴有水解缩合反应的种子乳液聚合动力学(I)模型

伴有水解缩合反应的自由基种子乳液聚合反应是制备有机-无机杂化乳胶粒的一种新方法，水解缩合反应和自由基聚合这两种反应在乳液体系中的动力学耦合过程决定了聚合产物的微结构和应用性质。通过单体的分配系数建立了单体在乳液体系中各相的分配模型，进而建立了考虑单体分配的自由基种子乳液共聚合的动力学模型。针对功能基团在乳液各相中水解缩合反应的特点，结合自由基种子乳液共聚合的动力学模型，建立了伴有水解缩合反应的自由基种子乳液聚合动力学模型。该模型反映了反应过程中的物质传递规律、非均相反应特点、自由基共聚合和水解缩合反应间的耦合关系。     

Preparation of crosslinked composite nanoparticles

Crosslinked composite nanoparticles were prepared by adding a trifunctional monomer (trimethyol propane trimethacrylate) or a difunctional monomer (divinyl benzene) as a crosslinker into the emulsion polymerization system of styrene in the presence of inorganic nanosilica. A coupling agent, 3‐methacryloxypropyltrimethoxysilane (MPS), was added along with the monomer, crosslinker, and silica to improve the interfacial interaction between silica and polymer and thus to obtain high binding efficiency. The role of MPS was examined. The effects of crosslinkers on the kinetics of emulsion polymerization, monomer conversion, and yield were investigated. The morphology of the composite particles was observed by TEM. The particle size and size distribution of composite latex particles were measured by the dynamic light scattering method. The binding efficiency and swelling ratio were determined by reluxing the sample in xylene using a Soxhlet extraction apparatus. FTIR spectra and TGA verified the participation of crosslinker and silica. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1538–1544, 2005     

Electron microscopic observation of uniform macroporous particles. II. Effect of DVB concentration

The electron microscopic observation of uniform and macroporous poly(styrene‐co‐divinylbenzene) particles prepared by a two‐step seeded polymerization method was performed. In the synthesis of uniform macroporous particles, the uniform polystyrene latices produced by a dispersion polymerization method with two different sizes and average molecular weights were utilized as the seed particles. The seed particles were first swollen with dibutylphthalate and then with a monomer phase, including styrene and divinylbenzene. The macroporous structure of the final particles was achieved by using a porogen mixture consisting of dibutylphthalate and linear polystyrene. The linear polystyrene part of the porogen solution was directly obtained from the seed latex. The macroporous particles with different diameters and porosities were produced by changing the divinylbenzene concentration between 25 and 100% in the repolymerization step. The effect of divinylbenzene concentration on the size and the surface morphology of the final particles were investigated by scanning electron microscopy. The internal structure of the final particles was analyzed by transmission electron microscopy. The results indicated that the average size of the final particles increased with the increasing divinylbenzene concentration. The increase in the DVB concentration also led to an increase in the average pore size. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2291–2302, 1999     

Morphology of poly(butyl acrylate)/poly(styrene‐co‐methyl methacrylate) latex prepared by starved emulsion polymerization: II. Development of particle morphology

Heterogeneous latexes were prepared by a two‐stage seeded emulsion polymerization process under monomer starved conditions at 80 °C using potassium persulfate as the initiator and sodium dodecyl sulfate as the emulsifier. Poly(butyl acrylate) latexes were used as seeds. The second‐stage polymer was poly(styrene‐co‐methyl methacrylate). By varying the amount of methyl methacrylate (MMA) in the second‐stage copolymer, the polarity of the copolymer phase could be controlled. It was found that the latex particles displayed different morphologies depending on the monomer ratio. The amount of MMA had a significant effect on the evolution of morphology. The morphologies were observed by transmission electron microscopy. In addition, the evolution of the particle morphology was predicted by the mathmatical model for cluster migration. The model gave the same trends as the experimental results. © 2002 Society of Chemical Industry     

Modeling the emulsion polymerization of amino-functionalized latex particles

A mathematical model for a semicontinuous seeded cationic emulsion polymerization was developed. The model includes the most distinctive features of the copolymerization of a cationic hydrophilic monomer with a hydrophobic one, including polymerization of the hydrophilic monomer in the outer shell of polymer particles and in the aqueous phase, and the possibility of having radical concentration profiles in the polymer particles.The reactions were carried out by means of a semicontinuous seeded cationic emulsion polymerization under starved conditions for styrene, which was the main monomer employed.The model predicts the evolution of the fractional overall conversions, the thickness of the outer shell, the total surface charge density and the partial conversions for the semicontinuous seeded cationic emulsion polymerization of styrene and aminoethyl methacrylate hydrochloride. Furthermore, the model can distinguish between the surface charge density provided by the cationic monomer than that given by the cationic initiator. Therefore, this model can predict the best conditions to obtain well-defined latexes with specific amounts of surface amino and amidine groups useful for immunoassays.     

Study on the effective process parameters influencing styrene and acrylonitrile grafting onto seeded polybutadiene latex

A series of experiments were designed and conducted to determine the significance of process parameters in the grafting of styrene and acrylonitrile onto polybutadiene seeds in a semicontinuous emulsion copolymerization system. The significances of the parameters were obtained by comparing the variance ratios, or F values, with F‐distributions. The significance level of each test (α‐value) was obtained by variance analysis. The important process parameters in industrial polymerization processes are usually monomer‐to‐polymer ratio, initiator type and concentration, chain‐transfer agent, and reaction temperature. The target responses were final monomer conversion, grafting degree, grafting efficiency, gel percent, and viscosity‐average molecular weight of free styrene‐acrylonitrile (SAN). The analysis of variance indicated that cumene hydroperoxide as the initiator and reaction temperature had strong effects on the graft structure. Moreover, free SAN molecular weight was significantly affected by the monomer/polymer ratio and cumene hydroperoxide and n‐dodecyl mercaptan as chain‐transfer agents. The raspberry‐like morphology of grafted acrylonitrile‐butadiene‐styrene (ABS) particles and phase separation within the particles were confirmed by transmission electron microscopy. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011