有机硅氧烷改性丙烯酸酯微乳液的合成与表征

采用种子乳液聚合法,以阴离子乳化剂DF-2和非离子乳化剂OP-10作为复合乳化剂,以FeSO4、K2S2O8和甲醛合次亚硫酸氢钠(SFS)作为氧化-还原引发剂,在65℃合成了有机硅改性丙烯酸酯聚合物微乳液。实验采用单体滴加工艺,用COULTERLS粒度仪和傅里叶变换红外光谱仪分别测定了共聚乳液的粒径分布和产物的结构,研究了加料方式、配方组成及操作方式对聚合稳定性、乳液的粒径分布以及产物性能的影响。结果表明,采用单体滴加工艺能得到平均粒径为50～80nm的单峰窄分布微乳液,并有效地将有机硅氧烷引入到共聚物大分子中。     

聚硅氧烷/聚丙烯酸酯共聚乳液的合成与表征

合成了含氢聚甲基硅氧烷／聚丙烯酸酯共聚乳液。研究了聚合工艺，配组成及操作方式对聚合稳定性，动力学，乳液的粒径分布和产物性能的影响。采用部分预乳化单体滴加法（工艺A）的部分纯单体滴加法（工艺B）两种工艺，聚硅氧烷采用高速预乳化滴加进料方式。用COULTER LS粒径仪和Nicolet傅立叶变换红外光谱仪分别测定共取乳液的粒径分布和产物的结构。研究结果表明，采用A，B两种工艺均能得到平均粒径为0.101-0.103μm的单峰窄分布共聚乳液，并能有效地将含氢聚硅氧烷引入了到共取物大分子中。含氢聚硅氧烷的引入量为3％（质量）时，共聚物涂膜具有柔软，滑爽和强度高等优点。     

有机硅、云母改性丙烯酸酯互穿网络阻尼材料的制备及性能研究

采用半连续乳液聚合的方法,在以丙烯酸酯类单体为主的二元互穿网络中加入有机硅单体与乳液进行共聚,得到了性能稳定的有机硅丙烯酸酯共聚乳液,并在乳液中加入了无机填料(绢云母)。考察了有机硅单体的用量对合成乳液及其胶膜性能的影响,通过红外光谱分析,证明了有机硅单体和丙烯酸酯单体的共聚。通过透射电镜(TEM)对乳胶粒子的观察,分析了有机硅单体及云母对乳液乳胶粒子形态结构的影响。通过动态粘弹仪(DMA)对材料的动态力学性能进行测试得到,Tanδ>0.3的温度范围为:-65～150℃。     

Silicone-polyacrylate composite latex particles. Particles formation and film properties

Composite latex particles with a polydimethylsiloxane PDMS core and a poly(methyl methacrylate-co-n-butyl acrylate) P(MMA-BA) copolymer shell were synthesized by seeded emulsion polymerization using the PDMS latex as the seed. The compatibility between the two polymer phases was changed by introducing vinyl groups in the latex core. Monomer conversions and particle size evolution were monitored to see the influence of the nature of the core functionality on the polymerization kinetics and on the extent of secondary nucleation. Particle morphology was characterized by cryo-transmission electron microscopy. The P(MMA-BA) copolymer formed a regular shell around the PDMS seed, whereas nonuniform coatings were formed when vinyl functionalities were introduced into the seed. Films were produced from the latexes, and their surface property was analyzed by X-ray photoelectron spectroscopy and contact angle measurements. It was shown that the PDMS component segregated to the polymer/air interface and that the extent of segregation depended on the original particles structure. Because PDMS has a very low glass transition temperature, it can easily diffuse throughout the film material. However, protected by an acrylic shell, polymer diffusion is significantly hindered and the film then displays all the characteristic properties of the acrylic copolymer. The surface composition of the films formed by the structured particles which PDMS core was not totally covered by the polyacrylate, was found to be intermediate between the composition of the films issued from the core-shell latexes and that of the films produced from blends of pure polyacrylate and PDMS latexes.     

用阴离子Gemini 9 B-6-9 B乳化剂合成苯乙烯-丙烯酸丁酯共聚物纳米乳液

以壬基酚、1,6-二溴己烷、氯磺酸为主要原料合成的阴离子Gemini磺酸盐表面活性剂9 B-6-9 B为乳化剂,苯乙烯(St)、丙烯酸丁酯(BA)为单体,合成了乳胶粒径小于100 nm且分布均匀的苯乙烯-丙烯酸丁酯共聚物纳米乳液,考察了聚合温度、乳化剂用量、引发剂用量、单体配比、单体含量对乳液的影响,探讨了乳胶粒子成核机理。结果表明,随着温度的升高,乳胶粒子的平均粒径减小,转化率与凝胶率增大;随着乳化剂或引发剂用量的增加,乳胶粒子的平均粒径和凝胶率减小,转化率增大;随着软单体比例的增加,乳胶粒子的平均粒径与转化率增大,粒径分布变宽,凝胶率减小;单体用量增大,乳胶粒子的平均粒径与凝胶率增大,转化率降低;乳胶粒子的粒径呈单峰分布,可能是按胶束成核机理形成的。     

Synthesis of well‐defined,functionalized polymer latex particles through semicontinuous emulsion polymerization processes

The design of a semicontinuous emulsion polymerization process, primarily based on theoretical calculations, has been carried out with the objective of achieving overall independent control over the latex particle size, the monodispersity in the particle size distribution, the homogeneous copolymer composition, the concentration of functional groups (e.g., carboxyl groups), and the glass‐transition temperature with n‐butyl methacrylate/n‐butyl acrylate/methacrylic acid as a model system. The surfactant coverage on the latex particles is very important for maintaining a constant particle number throughout the feed process, and this results in the formation of monodisperse latex particles. A model has been set up to calculate the surfactant coverage from the monomer feed rate, surfactant feed rate, desired solid content, and particle size. This model also leads to an equation correlating the polymerization rate to the instantaneous conversion of the monomer or comonomer mixture. This equation can be used to determine the maximum polymerization rate, only below or at which monomer‐starved conditions can be achieved. The maximum polymerization rate provides guidance for selecting the monomer feed rate in the semicontinuous emulsion polymerization process. The glass‐transition temperature of the resulting carboxylated poly(n‐butyl methacrylate‐co‐n‐butyl acrylate) copolymer can be adjusted through variations in the compositions of the copolymers with the linear Pochan equation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 30–41, 2003     

不同粒径含氟丙烯酸酯共聚乳液的合成及膜表面疏水性能研究

采用半连续种子乳液聚合的方式,以丙烯酸丁酯、甲基丙烯酸甲酯和甲基丙烯酸六氟丁酯为原料制备了粒径分别为30nm、75nm、210nm左右的含氟丙烯酸酯共聚物乳液。通过乳胶粒核壳结构设计与大小粒径乳液机械共混改性2种方法研究了如何在较少含氟单体用量的情况下达到较好的表面疏水性能。利用X射线光电子能谱、动态光散射仪、接触角测定仪等分析手段,研究了共聚物膜的表面性能和共聚物乳液粒径的大小及分布,测试结果表明,核壳结构乳液成膜后壳层含氟量较高,膜表面接触角大于90,°疏水性能强;而大小粒径乳液共混物成膜后表面含氟量较低,却仍能得到90°以上的接触角,表明乳胶膜表面具有粗糙结构,具有一定的仿荷叶效应。     

Preparation and characterization of stable and high solid content St/BA emulsifier-free latexes in the presence of AMPS

Stable and high solid content (about 50 wt%) St/BA emulsifier-free latexes were successfully synthesized using emulsifier-free emulsion polymerization with the addition of a small amount of reactive emulsifier AMPS. Properties of the latexes, such as the average particle diameter and its distribution, the morphology of latex particles, and stability were investigated. Physical properties of the latex films, i.e., glass transition temperature (T _g), water resistance, and solvent resistance were investigated as well. The size of latex particles is 400–600 nm in diameter, which is larger than that prepared by conventional emulsion polymerization. And the particle size distribution is narrow and uniform. It was found that the diameter of the latex particles decreases with the increasing content of the initiator KPS and the reactive emulsifier AMPS. Compared with the film prepared by conventional emulsion polymerization, water resistant and solvent resistant of the films prepared by emulsifier-free emulsion polymerization are improved greatly.     

Secondary nucleation of styrenated hydroxyl-functionalized latexes

In this study, secondary nucleation in emulsion polymerization of butyl acrylate (BA), styrene (St), and 2-hydroxyethyl methacrylate (HEMA), was investigated. Different molar ratios of BA and St were used. Average particle size, particle size distribution (PSD), polymerization kinetics, glass transition temperature (T_g), and surface tension were monitored and compared. All synthetic latexes were prepared through seeded semi-batch emulsion polymerization process. Three different BA to St ratios (1:1, 1:2, 2:1) were combined with eight different HEMA contents (0, 1, 3, 5, 10, 20, 30, 40 mol%) in monomer composition, respectively. In the case of high HEMA content (10–40 mol%) it is found that secondary nucleation is mainly affected by HEMA. Secondary nucleation at low HEMA content (1–5 mol%) is dependent on the BA to St monomer ratio, and consequently a reflection of z-mer hydrophobicity.     

In situ preparation and properties of high‐solid‐content and low‐viscosity poly(methyl methacrylate/n‐butyl acrylate/acrylic acid)/poly(styrene/acrylic acid) composite latexes

With monodispersed poly(methyl methacrylate/n‐butyl acrylate/acrylic acid) [P(MMA/BA/AA)] seeded latex with a particle size of 485 nm and a solid content of 50 wt % as a medium, a series of stable P(MMA/BA/AA)/poly(styrene/acrylic acid) composite latexes with a high solid content (70 wt %) and low viscosities (500–1000 mPa · s when the shear rate was 21 s^?1) was prepared in situ via simple two‐step semicontinuous monomer adding technology. The coagulum ratio of polymerization was about 0.05 wt %. The particle size distribution of such latexes was bimodal, in which the large particle was about 589 nm and the small one was about 80 nm. The latexes combined good mechanical properties with good film‐forming properties. Differential scanning calorimetry showed that the corresponding latex film had a two‐phase structure. The morphology of the latex film was characterized with atomic force microscopy and scanning electron microscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1815–1825, 2007     

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。     

Characterization and properties of gradient polyacrylate latex particles by gradient emulsion polymerization

In this study, gradient acrylate latex particles were synthesized by gradient copolymerization. n-Butyl acrylate (BA) and methyl methacrylate (MMA) were used as co-monomers, dodecyl diphenyl ether sodium disulfonate as the emulsifier, and potassium persulfate as the initiator. The technique involved the continuous addition of one monomer mixture into a stirred tank containing another monomer mixture. Their microstructure and properties were analyzed by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), atomic force microscopy (AFM), transmission electron microscopy (TEM), and particle size analysis. ¹H-NMR spectra show a gradual change in the chemical composition with the growth of molecular chains. The gradient polymer latexes, the instantaneous copolymer composition of which varies as the polymerization proceeds, are obtained. GPC analyses show that the aggregated molecular chain in the BA-centered latex particle experiences a process from dominant BA to MMA with changes in the monomer's feed composition during the polymerization. Particle size and TEM analyses show that the increasing latex size agrees well with the gradient growth pattern. DSC analyses show that the gradient latex particles exhibit only one broadened and ambiguous glass transition region. AFM analyses indicate no obvious microphase segregation occurs in the gradient latex particles, further verifying that the gradient microstructure is obtained.     

Synthesis and properties of Ricinodendron heudelotii oil based hybrid alkyd–acrylate latexes via miniemulsion polymerization

Ricinodendron heudelotii (R. heudelotii) oil-based novel alkyd–acrylate hybrid latexes were synthesized as waterborne environmental friendly binder for coating systems. Long oil length alkyd resins were synthesized by two-stage alcoholysis–polyesterification reaction with variation of phthalic anhydride (PA) and maleic anhydride (MAH) proportion and further polymerized with methyl methacrylate (MMA) and butyl acrylate (BA) via miniemulsion polymerization. It is found that increasing the proportion of MAH in the alkyd resin enhances monomer conversion and total solid content of the hybrid latex. The latexes exhibited fast drying time at room temperature. The prepared latexes showed a bimodal particle size distribution motion. It is shown that the increase in MAH content in the alkyd moiety has a significant effect on the improved performance properties of hybrid latexes as well as latex films including, fast drying time at room temperature, highly crosslinked network, improved mechanical characteristics before and after UV exposure, better shore A hardness and hydrophobic water repellency contact angle. The results suggested that, the R. heudelotii oil-based alkyd–acrylate hybrid latexes have potential improved properties for manufacture of waterborne coatings and are usable as an alternative to petroleum-based coating systems.     

Synthesis and characterization of butyl acrylate/methyl methacrylate/glycidyl methacrylate latexes

The butyl acrylate (BA)/methyl methacrylate (MMA), and glycidyl methacrylate (GMA) composite copolymer latex was synthesized by seeded emulsion polymerization technique taking poly(methyl methacrylate) (PMMA) latex as the seed. Four series of experiments were carried out by varying the ratio of BA : MMA (w/w) (i.e. 3.1 : 1, 2.3 : 1, 1.8 : 1, and 1.5 : 1) and in each series GMA content was varied from 1 to 5% (w/w). The structural properties of the copolymer were analyzed by FTIR, ¹H‐, and ¹³C‐NMR. Morphological characterization was carried out using transmission electron microscopy (TEM). In all the experiments, monomer conversion was ～99% and final copolymer composition was similar to that of feed composition. The incorporation of GMA into the copolymer chain was confirmed by ¹³C‐NMR. The glass transition temperature (T_g) of the copolymer latex obtained from the differential scanning calorimetry (DSC) curve was comparable to the values calculated theoretically. With increase in GMA content, particles having core‐shell morphology were obtained, and there was a decrease in the particle size as we go from 2–5% (w/w) of GMA. The adhesive strength of the latexes was found to be dependent on the monomer composition. With increase in BA : MMA ratio, the tackiness of the film increased while with its decrease the hardness of the film increased. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

微交联丙烯酸酯纳米乳液的制备及应用

用半连续种子乳液聚合工艺,合成了微交联丙烯酸酯纳米乳液。讨论了乳化剂、官能性单体、聚合温度及交联改性剂等因素对丙烯酸类聚合物乳液性能的影响。研究结果表明,用本工艺当乳化剂质量分数为2%,N 羟甲基丙烯酰胺质量分数低于0 4%,聚合温度为75～85℃时,可得到平均粒径为49 6nm,多分散性指数为0 149的单峰宽分布丙烯酸酯共聚乳液,将其用于皮革的填充,可显著改善皮革的柔软性、弹性以及革面的手感。     

超声辐照废聚苯乙烯泡沫／丙烯酸丁酯共聚乳液研究

以十二烷基硫酸钠和壬基酚聚氧乙烯醚为乳化剂,在超声波作用下合成了聚苯乙烯（PSt）与丙烯酸丁酯（BA）的共聚乳液．研究了聚合方法、超声波强度、环境温度、聚合物浓度对单体转化率的影响,透射电镜图表明,乳液粒子有核壳结构,粒径分布呈多分散型,由此可以推测该乳液的成核方式是液滴成核．     

Preparation and characterization of self-crosslinking fluorinated polyacrylate latexes and their pressure sensitive adhesive applications

Self-crosslinking fluorinated polyacrylate latexes based on butyl acrylate (BA), fluorine monomer octafluoropentyl methacrylate (OFPMA), self-crosslinking functional monomers acrylic acid (AA) and 2-hydroxyethyl acrylate (HEA) were synthesized by a monomer-starved seeded semi-continuous emulsion polymerization process. The latexes and their corresponding films were characterized by laser particle size analyser, Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), contact angle goniometer, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Results indicated that the particle size of the latexes and the gel content of the films were both independent of the amount of OFPMA employed. On the other hand, the particle size of the latexes decreased and the gel content of the films increased with the incorporation of AA and HEA as expected. Glass transition temperature (T_g) and the thermal stability of the copolymer were both improved gradually as OFPMA content increased. XPS, AFM and water contact angle measurement indicated that the fluoroalkyl groups had a tendency to enrich on the surface of the films. However, this enrichment of fluorine on the film surface was reduced after the introduction of self-crosslinking functional monomers into the system. Finally, the adhesive property of the latexes was evaluated for application as a pressure sensitive adhesive (PSA).     

Structure and mechanical properties of the hybrid films of well dispersed SiO2 nanoparticle in polyimide (PI/SiO2) prepared by sol–gel process

Methyl methacrylate-butyl acrylate structural latexes were synthesized by two-stage seeded emulsion polymerization using 1,1-diphenylethylene (DPE) as a control reagent. In the first stage, the seed latex particles with the precursor poly (methyl methacrylate-DPE) (P(MMA-DPE)) were prepared, and then the second monomer n-butyl acrylate (nBA) was swollen into the seed latex particles under stirring at room temperature. In the second stage, the polymerization of nBA was thermally initiated at 80 °C, and the latex particles composed of block copolymer were synthesized. The size and morphology of the latex particles were investigated by light scattering and TEM. The contact angles of different latex films were also measured. The block copolymer was characterized by size exclusion chromatography, nuclear magnetic resonance spectroscopy, and differential scanning calorimetry. Microphase separation of the block copolymer was examined using atomic force microscopy.     

丙烯腈与丙烯酸乙酯乳液共聚合及其表征

用氧化还原引发体系在低温下研究了丙烯腈与丙烯酸乙酯的乳液共聚合。考察了聚合温度、乳化剂浓度和分子量调节剂浓度对聚合的影响 ,结果表明 ,随温度升高 ,乳化剂浓度增大 ,单体转化率和分子量增大 ,乳液更稳定 ;链转移剂十二烷基硫醇浓度增加 ,分子量显著降低 ,转化率有所降低 ,表明十二烷基硫醇在调节分子量的同时也起着缓聚剂的作用。用激光粒径分析仪考察了 2 0℃时聚合过程中乳胶粒子大小的变化 ,发现聚合过程的成核和增长均在胶束中进行的。用凝胶渗透色谱法研究了十二烷基硫醇对聚合物分子量的影响 ,发现聚合时加入分子量调节剂 ,活性链寿命较短并呈单峰分布 :聚合时不加入分子量调节剂 ,活性链寿命较长并呈双峰分布。 DSC结果表明 ,随聚合体系中软单体含量增加 ,共聚物的玻璃化温度降低。     

乙酸乙烯酯-丙烯酸异辛酯-乙烯基乙酰氧基硅烷的乳液聚合

制备了乙酸乙烯酯-丙烯酸异辛酯(2-EHA)-乙烯基乙酰氧基硅烷三元共聚胶乳,研究了聚合工艺、乳化剂、保护胶和2-EHA质量分数对共聚反应、胶乳性能及共聚物性能的影响。结果表明,该乳液聚合体系中,预乳化工艺明显优于半连续法工艺;当以十二烷基硫酸钠／聚乙二醇辛基苯基醚为复合乳化剂、以聚乙烯醇为保护胶时,聚合反应平稳,所得胶乳具有很好的稳定性;随着2-EHA质量分数的增加,胶乳稳定性逐渐提高,共聚物的玻璃化转变温度和胶乳的最低成膜温度降低,但2-EHA对前者的影响明显大于对后者的影响;乳胶膜的吸水量在200h后达到饱和。