Effect of hydrogenated acrylic rosin on structure and properties of polyacrylates emulsions by seeded semibatch emulsion polymerization method

Hydrogenated acrylic rosin (HAR)/polyacrylate composite emulsions were prepared by seeded semibatch emulsion polymerization method. The effect of HAR amount on monomer conversion rate, coagulum rate, and gel fraction of the composite emulsions as well as the water absorption ratio, adhesion properties, and thermal durability of the HAR/polyacrylate composite latex films was studied; the composites were also characterized by Fourier transform infrared spectroscopy (FT-IR), gel permeation chromatograph (GPC), differential scanning calorimetry, and thermogravimetry. The results showed that with the increase of HAR amount, the monomer conversion rate, gel fraction, molecular weight, and water absorption ratio were all decreased, and the coagulum rate and molecular weight distribution increased. HAR had good compatibility with polyacrylate, and when HAR amount was 4 wt%, the HAR/polyacrylate composite latex film had superior adhesion properties and thermal durability.     

In situ synthesis and properties of hydrogenated rosin/polyacrylate composite miniemulsions-based pressure sensitive adhesives

Hydrogenated rosin/polyacrylate composite miniemulsions-based pressure sensitive adhesives were synthesized by in situ miniemulsion polymerization method. The effect of HR amount on the monomer conversion rate, particle size and its polydispersity, coagulum rate, Zeta potential, and stability of the composite miniemulsions were studied, the effect of HR and crosslinker amount on the adhesion properties of the composite latex films were also investigated, and the composites were characterized by differential scanning calorimetry (DSC) and gel permeation chromatograph. The results showed that with HR amount increasing, the monomer conversion rate decreased, and the absolute value of Zeta potential and the molecular weight of the sol in the composite latex films also decreased, while the particle size and its polydispersity were almost unaffected. DSC analysis indicated that HR had relative good compatibility with polyacrylate. However, excess HR amount led to the decrease of the centrifugal stability and storage stability of the composite miniemulsions. Furthermore, with HR amount increasing, the ball tack of the latex films increased gradually, 180^o peel strength first increased and then decreased, and holding force decreased constantly. When HR amount exceeded 10 wt%, the failure style changed from interface failure to cohesion failure. The crosslinker CX-100 was helpful for the improvement of 180^o peel strength and holding force. When HR and CX-100 amount were 10 and 0.6 wt%, the ball tack, 180^o peel strength, and holding force were 9 #, 8.9 N/25 mm, and 178 h, respectively.     

氢化丙烯酸松香/丙烯酸酯复合乳液的制备及其压敏胶的性能

以氢化丙烯酸松香为增黏树脂,将其溶解在丙烯酸酯单体中,预乳化后采用半连续乳液聚合工艺制备了氢化丙烯酸松香/丙烯酸酯复合乳液。研究了氢化丙烯酸松香的用量对单体转化率、凝胶率、溶胶相对分子质量及其分布、乳胶膜的玻璃化温度(Tg)和压敏胶粘接性能等的影响。结果表明,氢化丙烯酸松香对单体聚合具有一定的阻聚作用,随着氢化丙烯酸松香用量的增加,单体转化率、凝胶率及相对分子质量下降,相对分子质量分布变窄。氢化丙烯酸松香的合适用量为8.0%wt,此时压敏胶的初黏力为15#,180°剥离强度为10.6N.25mm-1,持黏力大于120h。     

Preparation and characterization of waterborne epoxy latexes and epoxy/(silica sol) composites

A series of waterborne epoxy latexes was synthesized, and epoxy/(silica sol) composite latexes were prepared. The effects of functional monomer methacrylic acid (MAA) and silica sol on the latex particle size, morphology, and stability were investigated. With increasing amounts of MAA, the conversion rate increased, the particle size reduced, and the viscosity of the epoxy latexes increased. The epoxy latexes had storage stability and could be stored at room temperature for more than 6 months with a solid content variation of less than 1%. For the (silica sol)‐modified waterborne epoxy latexes, the effects of preparation techniques and silica sol content on the latexes and latex films were investigated. When the silica sol content increased, the particle size of the composite latexes decreased. The morphology investigation showed that when the silica sol content increased, the uneven surface level of the latex films was increased. The increase of elemental silica on the surface was in accord with the improvement of the water resistance of the composite latex films. The heat resistance of these films was improved as well, and their overall performance was better than that of the epoxy latex films. J. VINYL ADDIT. TECHNOL., 20:57–64, 2014. © 2014 Society of Plastics Engineers     

Superparamagnetic latex synthesized by a new route of emulsifier‐free emulsion polymerization

The aim of this study was to design polymeric nanospheres containing magnetic nanoparticle which could display superparamagnetic behavior and thus find application in allied fields. First magnetite nanoparticles were synthesized with coprecipitation method and then their stable acidic dispersion was prepared without surfactant and dropped into the polymerization system during a certain time interval after the polymerization started. The effects of time at which the magnetic sol was added into polymerization system on latex size and stability, average molecular weight of polymer were examined in the case of two different monomer concentrations. Extensive characterization by transmission electron microscopy, dynamic light scattering, thermal gravimetric analysis and magnetic measurements shows that when the magnetic sol was dropped during earlier time of polymerization at stage 1, the latex size, average molecular weight of polymer, thermal stability of polymeric composite, and saturation magnetization reduced, whereas polydispersity of size and molecular weight increased because of the reaction between persulfate and naked surface of magnetite at the aqueous phase. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

核壳结构聚硅氧烷/丙烯酸酯复合乳液(Ⅰ)乳化剂对乳液聚合过程及粒径分布和粒子形态的影响

采用种子乳液半连续法合成了具有高有机硅含量的聚硅氧烷/丙烯酸酯核壳结构复合乳液,研究乳化剂的种类、复配比例及质量浓度对有机硅／丙烯酸酯壳核乳液性能与乳胶粒径、分布和结构的影响.结果表明：阴离子乳化剂十二烷基硫酸钠(SDS)、十二烷基磺酸钠(SDS-2)、十二烷基苯磺酸钠(SDBS)所合成的乳胶粒子粒径依次增大,SDS与非离子型乳化剂OP-10复配使用时,随OP-10质量分数的增加,聚合速率和转化率降低,化学稳定性增加,乳胶粒子粒径增大,分布变宽,确定了复合乳化剂的最佳配比.随复合乳化剂浓度的增加,聚合速率加快、转化率增加,乳胶粒子粒径减小而分布加宽.通过改变乳化剂加入方式可减小乳胶粒子的粒径分布.为减少壳层聚合物新粒子的产生,需严格控制乳化剂的浓度,使加入的壳层单体处于“饥饿”状态,在乳胶粒子表面富集、引发聚合,形成表层“过渡层”,最终形成核壳结构复合粒子.     

细乳液聚合制备改性硅溶胶／聚丙烯酸酯复合乳液

常温下一步法制备改性硅溶胶,并通过细乳液聚合制备改性硅溶胶／聚丙烯酸酯复合乳液。考查了温度对聚合速率和单体转化率的影响以及不同乳化剂含量下聚合过程中乳胶粒粒径的变化情况;测试了乳胶膜的吸水率,并用接触角法表征了乳胶膜的表面自由能。     

剥离型蒙脱土/复合苯丙乳液的制备及其性能研究

在剥离态Na-MMT（钠基蒙脱土）悬浮液中,以原位乳液聚合法制备剥离型Na-MMT/苯丙复合乳液,通过红外光谱表征复合乳液的组成,研究了Na-MMT含量对复合乳液乳胶粒粒径、转化率、聚合稳定性和存稳定性的影响,通过热重和吸水率表征Na-MMT/苯丙复合乳液的抗水性和耐热性。实验结果表明：Na-MMT质量分数在3.0%以内有利于制备得到稳定性良好的复合乳液,复合乳液乳胶粒粒径和复合乳液涂膜吸水率均先减小后增大,Na-MMT质量分数为3.0%的复合乳液耐热性比苯丙乳液提高30℃。     

A new concentrated emulsion polymerization pathway

To ensure the stability of the concentrated emulsions that are employed as precursors for polymerization, a two-step concentrated emulsion polymerization pathway is described. In the first step, the monomer is partially polymerized by heating at 50°C until a certain conversion is reached. Subsequently, the partially polymerized monomer is used as the dispersed phase to prepare a concentrated emulsion in which water constitutes the continuous phase. The concentrated emulsion has a large volume fraction of the dispersed phase (0.74–0.99) and the appearance of a gel. Several typical monomers are employed to correlate the stability of the concentrated emulsion and the extent of partial polymerization of the dispersed phase. It was found that monomers, which cannot lead to stable concentrated emulsions, can generate them after partial polymerization. Subsequent polymerization of the concentrated emulsion leads to latex particles. Copolymers and polymer composites were also prepared by the two-step procedure. In the latter case, water was replaced with a solution of a hydrophilic monomer in water as the continuous phase. © 1992 John Wiley & Sons, Inc.     

Facile fabrication and modification of polyacrylate/silica nanocomposite latexes prepared by silica sol and silane coupling agent

Polyacrylate/silica nanocomposite latexes were prepared by silica sol and facilely modified with a silane coupling agent γ-methacryloxypropyltrimethoxysilane (KH-570) aimed at reinforcing the interaction between silica nanoparticles and latex particles in a convenient way. The effects of silica sol and KH-570 amounts on the performance of latexes and films are discussed. Particle size and morphology tests demonstrated that the silica nanoparticles could form hydrogen bond interactions between latex particles, and thus influence the rheological properties of latexes. Tensile measurements and SEM photographs showed the reinforcing and toughening roles of silica nanoparticles. SEM images also indicated that the addition of silica sol increased the roughness of films, which resulted in the increase of hydrophilic silanol groups on the film surface and the decrease of water resistance of latex films. The latex films retained good adhesion force, flexibility, and impact resistance even when the silica sol content was as much as 25%. TGA data revealed that the incorporation of silica sol enhanced the thermal stability of the films. After introducing KH-570, the particle size increased with the increase of the amount of KH-570. Moreover, the addition of KH-570 improved the water resistance and maintained other properties of the latex films appropriately.     

原位乳液聚合制备聚合墨粉用含蜡苯丙复合乳液及其性能研究

采用核壳乳液聚合的方法,以苯乙烯、丙烯酸丁酯和丙烯酸为共聚单体,原位制备了聚合墨粉用含蜡苯丙复合乳液。探讨了巴西棕榈蜡用量对单体转化率、凝聚率、复合乳液粒径及其分布、Zeta电位、共聚物的玻璃化转变温度以及相对分子质量及其分布的影响。结果表明,巴西棕榈蜡的加入对聚合稳定性影响不大;随着其用量的增加,乳液粒径、Zeta电位、聚合物玻璃化转变温度降低,而相对分子质量增大。当其用量为3%(wt)时,聚合物具有较适宜的Tg和相对分子质量,分别为65.9℃和89,000。     

Preparation and properties of poly[styrene‐co‐(butyl acrylate)‐co‐(acrylic acid)]/silica nanocomposite latex prepared using an acidic silica sol

BACKGROUND: Polyacrylate/silica nanocomposite latexes have been fabricated using blending methods with silica nanopowder, in situ polymerization with surface‐functionalized silica nanoparticles or sol–gel processes with silica precursors. But these approaches have the disadvantages of limited silica load, poor emulsion stability or poor film‐forming ability. RESULTS: In this work, poly[styrene‐co‐(butyl acrylate)‐co‐(acrylic acid)] [P(St‐BA‐AA)]/silica nanocomposite latexes and their dried films were prepared by adding an acidic silica sol to the emulsion polymerization stage. Morphological and rheological characterization shows that the silica nanoparticles are not encapsulated within polymer latex particles, but interact partially with polymer latex particles via hydrogen bonds between the silanol groups and the ? COOH groups at the surface of the polymer particles. The dried nanocomposite films have a better UV‐blocking ability than the pure polymer film, and retain their transparency even with a silica content up to 9.1 wt%. More interestingly, the hardness of the nanocomposite films increases markedly with increasing silica content, and the toughness of the films is not reduced at silica contents up to 33.3 wt%. An unexpected improvement of the solvent resistance of the nanocomposite films is also observed. CONCLUSION: Highly stable P(St‐BA‐AA)/silica nanocomposite latexes can be prepared with a wide range of silica content using an acidic silica sol. The dried nanocomposite films of these latexes exhibit simultaneous improvement of hardness and toughness even at high silica load, and enhanced solvent resistance, presumably resulting from hydrogen bond interactions between polymer chains and silica particles as well as silica aggregate/particle networks. Copyright © 2009 Society of Chemical Industry     

Radiation grafting of methyl methacrylate monomer on natural rubber latex

A method of radiation grafting of methyl methacrylate (MMA) monomer on natural rubber (NR) latex has been studied. The irradiation dose in radiation emulsion polymerization of MMA monomer was lower compared to the irradiation dose for grafting of MMA monomer on NR latex, in order to obtain the same degree of conversion. This is due to the size of the rubber particles which are quite large and, hence, not sufficient to ensure an ideal emulsion polymerization. The irradiation dose for radiation grafting of MMA monomer on latex was around 300 krad to obtain a 75% degree of conversion. However, this irradiation dose was lower compared to the irradation dose for bulk polymerization of MMA monomer, in order to obtain the same degree of conversion. This is due to the gel effect in the viscous media. Radiation grafting of MMA monomer on NR latex does not influence the pH of the latex, but influences the viscosity significantly. The viscosity of the NR latex increased with an increase in irradiation dose, due to the increase of the total solid content in the latex. The MMA monomer converted to P-MMA in NR latex was largely grafted on the NR, or at least insoluble in a solvent for P-MMA, such as acetone or toluene. The hardness of the pure gum vulcanizate with an increase in the degree of grafting or P-MMA content, but the other physical properties, such as tensile strength, modulus, elongation at break, and thermal stability, were not greatly influenced by the degree of grafting.     

Preparation and characterization of polysiloxane–polyacrylates composite latices and their film properties

Gamma‐ray induced seeded emulsion polymerization of methyl methacrylate and butyl acrylate was carried out in the presence of a polymerizable polysiloxane seed latex, obtained by ring‐opening copolymerization of octamethyl cyclotetrasiloxane (D₄) and tetramethyl tetravinyl cyclotetrasiloxane (VD₄), catalyzed by dodecylbenzene sulfonic acid (DBSA). A series of polysiloxane seed latices with different molecular weights, vinyl contents and particle sizes was used. The conversion–time curve showed that the polymerization rate was accelerated significantly by the seed latex. The obtained composite latices also showed good storage stability, mechanical stability and high electrolyte resistance ability. By using transmission electron microscopy (TEM), the morphology of the composite latex particles was found to display a quite uniform fine structure. The graft polymerization reactions between the polymerizable polysiloxane and the acrylates were confirmed by Fourier‐transform infrared spectroscopy (FT‐IR) and the graft efficiencies were also studied. The influence of seed content, molecular weight, vinyl content of the polysiloxane and seed latex particles size on the mechanical performance, water absorption ratio, surface properties and transparency of the latex films was also investigated. It was found that the seed content and particles size greatly affect the mechanical performance, water absorption ratio and transparency of the latex films. Copyright © 2005 Society of Chemical Industry     

可聚合阳离子含氟表面活性剂在含氟丙烯酸酯乳液聚合中的应用

以可聚合阳离子含氟表面活性剂N-(乙酸全氟辛基乙基酯)-N-(乙醇丙烯酸酯)二甲基溴化铵(PF8DM)为乳化剂,进行含氟丙烯酸酯的细乳液聚合研究,考察了PF8DM用量对单体转化率和凝胶率的影响,PF8DM用量对乳液的稳定性和表面性能的影响;分别采用PF8DM和十六烷基三甲基溴化铵作为乳化剂考察其对乳胶膜性能的影响。结果表明,当PF8DM含量为单体总质量的4%时,单体转化率达95%,凝胶率为0.6%;所得乳液具有优异的贮存、稀释、离心稳定性;当PF8DM用量为单体总质量的6%时得到的乳胶膜接触角达118.6°。在总含氟量相同的条件下,采用PF8DM为乳化剂制备的含氟丙烯酸酯乳液,其乳胶膜的吸水率大大降低,拒水性也明显增强。     

微滴乳液聚合制备PDMS/SiO2纳米复合材料

采用超声分散的方法,以少量八甲基环四硅氧烷(D₄)对硅溶胶粒子进行表面接枝改性。然后在改性硅溶胶存在下,以十二烷基苯磺酸(DBSA)为乳化剂兼催化剂进行D₄的微滴乳液聚合,得到聚硅氧烷(PDMS)/二氧化硅(SiO₂)纳米复合乳液。采用FTIR、TGA、纳米粒度仪、TEM和拉力机分别对样品进行了表征。结果表明:采用超声分散的方法,能够有效地实现硅溶胶粒子的表面改性。通过微滴乳液聚合得到的复合乳胶粒是聚合物包覆二氧化硅粒子的核壳结构形态。SiO₂的引入提高了有机硅复合膜力学性能,增强了热稳定性。     

含缩水甘油基／氨基丙烯酸酯共聚物乳液的聚合稳定性

研究了乳胶粒组成对含有缩水甘油基,羧基和胺基的丙烯酸酯多层核壳型乳液聚合稳定性的影响规律,探讨了聚合过程的凝聚机理。研究表明：官能团间的交联凝聚作用和水溶性聚合物的架桥凝聚作用是本体系凝聚物形成的主要原因。     

Effect of Long-Chain Acrylate on the Properties of Polyacrylate/Nano-SiO2 Composite Leather Finishing Agent

Polyacrylate/nano-SiO₂ composite leather finishing agent was prepared via emulsion polymerization with butyl acrylate, methyl methacrylate, lauryl methacrylate as the main raw materials. The effects of different polymerization processes, lauryl methacrylate on the properties of composite were studied. The results show pre-emulsified emulsion polymerizations obtain a lower gel rate and higher conversion rate. Adding lauryl methacrylate can improve the water resistance, physical and mechanical properties of the composite film. Leather finished with P(Butyl acrylate/Methyl methacrylate/Lauryl methacrylate)/nano-SiO₂ composite latex show lower water-vapor permeability, lower water uptake and better resistence to the external force than that of the leather finished with P(Butyl acrylate/Methyl methacrylate)/nano-SiO₂ composite latex.     

醋酸乙烯-丙烯酸无皂乳液共聚的研究

研究了以醋酸乙烯(VAc)为主单体,丙烯酸(AA)为改性功能单体,以“半连续”加料方式进行无皂乳液共聚合过程,得到了稳定的乳液。并探讨了功能单体AA含量、反应温度等对共聚的影响。采用FTIR、粒度分析等方法对共聚物的组成、乳胶粒子的尺寸及分布进行了分析表征。结果表明:在(65±2)℃的温度下聚合,所得乳液稳定性好、转化率高,反应完全,且随着功能单体AA含量的增加,乳液粘度上升,单体转化率下降,乳胶粒粒径变小且粒径呈单分散性。     

Controlled preparation and properties of acrylic acid epoxy-acrylate composite emulsion for self-crosslinking coatings

A stable epoxy-acrylate composite latex was successfully prepared through emulsion polymerization of modified epoxy acrylic (EPAC) oligomer with acrylate monomer. The EPAC oligomer was obtained using active acrylic acid (AA) to react with epoxy resin. And by regulating the reaction degree of the active hydrogen of AA and epoxide group, there is the acquisition of terminal double bond that gives EPAC reactivity, together with the partial retention of the epoxide group that enables self-crosslinking during film formation. The structural conformation of the oligomer was ascertained by Fourier transform infrared (FTIR) spectroscopy. The factors influencing the stability of the epoxy-acrylate composite latex were investigated. The epoxy-acrylate composite latex was the most stable when methyl acrylic acid was 1.5 wt% and modified EPAC oligomer was 15 wt% of the total monomer weight. The morphology and property of the composite latex films were characterized by scanning electron microscopy, transmission electron microscopy (TEM), and temperature-modulated differential scanning calorimetry (TOPEM-DSC). The results confirm that there is successful emulsion copolymerization between modified EPAC oligomer and acrylate monomer. TEM show that the particles of epoxy-acrylate composite have a core-shell structure, and there is no free epoxy resin. The FTIR and TOPEM-DSC results reveal that the copolymer emulsion possesses self-crosslinking ability. During film formation, self-crosslinking reaction occurs between epoxide groups with carboxyl groups, giving exothermal phenomena. The thermal stability as well as the corrosion resistance of the films was analyzed. The results show outstanding thermal stability as well as corrosion resistance attributable to the crosslinking reticulation structure. It is envisaged that the epoxy-acrylate composite latex has great potential in the development of high-performance aqueous coatings.