Synthesis and characterization of new polysiloxane bearing vinylic function and its application for the preparation of poly (silicone-co-acrylate)/montmorillonite nanocomposite emulsion

A new silicone containing acrylic monomer, methacryloxyethyl polymethylhydrosiloxane ether (MEPMHSE), based on polymethylhydrosiloxane (PMHS) and 2-hydroxyethyl methacrylate (HEMA) has been synthesized for formulation of nanocomposite emulsion. Then Poly (silicone-co-acrylate)/montmorillonite (PSAM)/nanocomposite emulsion were prepared by in situ intercalative emulsion polymerization of methyl methacrylate (MMA), butyl acrylate (BA), methacrylic acid (MAA) and MEPMHSE, in the presence of organic modified montmorillonite (OMMT) with different OMMT contents (0, 0.5, 1.0, 1.5 and 2 wt%) and auxiliary agents in the presence of potassium persulphate (KPS) as initiator. Alkylphenol ethersulphate and Arkupal N-300 were used as anionic and non-ionic emulsifiers, respectively. The resulting monomer was characterized by Fourier transformer infrared spectroscopy (FTIR), proton (¹H NMR), and carbon (¹³C NMR) nuclear magnetic resonance spectroscopes. The OMMT was characterized by FTIR and X-ray diffraction (XRD). The nanocomposite emulsions were characterized by using Fourier transform infrared spectroscopy (FTIR), laser light scattering and surface tension. Thermal properties of the copolymers were studied by using thermogravimetric analysis (TGA) and dynamic mechanical thermal analysis (DMTA) and then the effects of OMMT percent on the water absorption ratio and drying speed were examined. Results showed that OMMT could improve the properties of emulsion, in other words, the properties of nanocomposite emulsion were better when compared with those of the silicone–acrylate emulsion. The property of nanocomposite emulsion containing 1 wt% OMMT was the best one, and the following advantages were obtained: smaller particle size, faster drying speed, smaller surface tension, and improved resistant water by the incorporation of OMMT.     

Preparation and properties of poly(silicone‐co‐acrylate)/montmorillonite nanocomposite emulsion

Poly (silicone‐co‐acrylate)/montmorillonite nanocomposite emulsion were prepared by in situ intercalative emulsion polymerization of acrylate and organosilicone, in the presence of organic modified montmorillonite (OMMT) with different OMMT contents (0, 0.5, 1, 1.5, and 2 wt %). The nanocomposite emulsions were characterized with X‐ray diffraction (XRD), laser light scattering, fourier transform infrared (FTIR), rheological measurements, surface tension, drying speed, and water absorption property. Results showed that OMMT could improve the properties of emulsion, in other words, the properties of nanocomposite emulsion were better when compared with those of the silicone–acrylate emulsion. The properties of nanocomposite emulsion containing 1 wt % OMMT was the best one, and obtained the following advantages: smaller particle size, faster drying speed, shorter curing time, smaller surface tension, bigger apparent viscosity, and improved resistant water by the incorporation of OMMT. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3963–3970, 2006     

相转移催化法合成烯丙基缩水甘油醚

以烯丙醇和环氧氯丙烷为原料，采用相转移催化法，合成了烯丙基缩水甘油醚。研究了反应时间、反应温度、投料比及固体碱的用量对反应收率的影响。在n(烯丙醇)∶n(环氧氯丙烷)∶n(固体碱)∶n(催化剂)=1∶1.5∶1.5∶0.005、反应时间1 h、反应温度50～60 ℃时，烯丙醇缩水甘油醚收率可达88%。     

烯丙基-联苯醚的合成及其共聚合

采用相转移催化法合成了一种新型的非离子型疏水单体烯丙基-联苯醚(ABE),通过傅里叶变换红外光谱、核磁共振氢谱等表征了单体的结构,并分别用乳液法和溶液法合成了ABE-丙烯酰胺(AM)-丙烯酸(AA)三元共聚物。溶液法合成的共聚物为细小颗粒,平均粒径为900 nm左右,比表面积为14.93 m2/g,水溶性较差;而乳液法制备的共聚物水溶性较好,特性黏数大,达37.69 dL/g,耐热性能优良。     

硅烷偶联剂改性核壳丙烯酸酯乳液合成

以甲基丙烯酸甲酯（MMA）、苯乙烯（St）和丙烯酸丁酯（BA）为主单体,硅烷偶联剂为改性单体,制备出“软核硬壳”粒子的核壳结构丙烯酸酯乳液。设计结构,探究交联单体对乳液性能的影响。结果表明：当苯乙烯的质量分数为15%（以全部单体的总质量为基准,下同）,核层与壳层的理论玻璃化温度（Tg）分别为-10 ℃和30 ℃,核层交联单体乙烯基三乙氧基硅烷（A-151）和壳层交联单体γ-甲基丙烯酰氧基丙基三甲氧基硅烷（A-174）的用量分别为3%和2%时,乳液的稳定性和成膜性较好。对比未加交联单体的均相粒子结构,核壳结构聚合物的最大热粘温度提高90 ℃,吸水率降低10.8%,热分解温度（质量损失5%）提高38 ℃,缓解了水墨涂层的高温回粘问题,提高了涂膜的耐水性和耐热性。     

聚醋酸乙烯/蒙脱土纳米复合乳液涂层的耐蚀性研究

通过单体原位插层半连续乳液聚合法制备了聚醋酸乙烯酯/蒙脱土(PVAc/MMT)纳米复合乳液,分别对PVAc/MMT和PVAc乳液涂层在紫外环境、湿热环境和自然环境三个条件下进行腐蚀研究。结果表明,PVAc/MMT纳米复合乳液涂层表现出优异的的性能,是一种理想的制备乳胶漆的乳液。     

Synthesis and photo‐curing behaviors of silicon‐containing (vinyl ether)–(allyl ether) hybrid monomers

A series of silicon‐containing (vinyl ether)–(allyl ether) hybrid monomers used in nano‐imprint lithography resists were synthesized and subjected to photo‐initiated polymerization. The surface energies of the monomers and the resulting polymer films were then investigated. The surface energies of the monomers were very low at less than 15 mJ m^–2. The photo‐curing behaviors of the five hybrid monomers were investigated using real‐time Fourier transform infrared spectroscopy. The monomers were sequentially initiated with cationic (PAG201) and mixed (cationic initiator PAG201, radical initiator ITX or TPO) initiators. The vinyl ether double bond polymerized both rapidly and completely, whereas the allyl ether double bond remained when PAG201 was used as the photo‐initiator and polymerized completely with mixed initiators. The different double bonds of the silicon‐containing (vinyl ether)–(allyl ether) hybrid monomer increased the efficiency of the polymerization and overcame the intrinsic limitations of the free radical and cationic polymerization processes, including strong oxygen inhibition, large volume shrinkage and high humidity sensitivity. The five monomers with low viscosity, low surface energy, good thermal stability and good photo‐polymerization properties were suitable for nano‐imprint photoresists. © 2013 Society of Chemical Industry     

有机硅改性丙烯酸酯乳液聚合及应用研究

摘要：采用乳液聚合方式合成有机硅改性丙烯酸酯类涂料印花粘合剂,讨论各种因素对乳液聚合的影响。结果显示,该粘合剂具有良好的性能,整理后的织物摩擦牢度、皂洗牢度、手感等各项指标优良。     

Preparation of poly(styrene‐co‐butyl acrylate)/montmorillonite nanocomposite by emulsion polymerization: Characterization and nanoscratch behavior

Organic–inorganic hybrid poly(styrene‐co‐butyl acrylate)/organically modified montmorillonite (PSBA/organo‐MMT) latex particles have been prepared by in situ emulsion polymerization. The effects of modifier variety and the level of organo‐MMT have been investigated on the basis of the characteristics and mechanical properties of the resulting hybrid emulsion polymers. Although the more hydrophilic intercalated organic modifiers increased the latex particle size, the hydrophobic ones decreased the particle size. A more heterogeneous copolymer chain intercalation was seen by widespread XRD reflection as the organo‐MMT (organoclay) level increases. The tapping mode atomic force microscopy (AFM) and transmission electron microscopy (TEM) were used to determine the dispersion state of organoclay particles inside the nanocomposite copolymer films. Dynamic mechanical thermal analysis (DMTA) showed that adding the organoclay to the copolymer decreased the maximum loss tangent (tanδ) value and caused the shift to a lower temperature. Interestingly, the incorporation of organoclay decreased the glass storage modulus of the copolymer, while increased the rubbery storage modulus to some extent. In addition, a standard indenter for the nanoscratching of copolymer nanocomposite films was used under low applied loads of 150 and 250 μN. The nanoscratch results showed that incorporation of a 3 wt % hydrophobic organoclay, e.g., Closite15A, in the copolymer matrix enhanced considerably the near‐surface hardness and grooving resistance of the nanocomposite film at room temperature. In fact, copolymer nanocomposite films with higher near‐surface hardness and tanδ curve broadening exhibited more nanoscratch resistance through a specific variety of viscoelastic deformation, which did not create a bigger groove. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

氟硅丙烯酸酯/钠基蒙脱土复合乳胶涂层的制备及防腐蚀性能

以甲基丙烯酸十二氟庚酯和乙烯基三甲氧基硅烷为功能单体,采用种子乳液聚合法合成氟硅丙烯酸酯乳液(氟硅),然后将钠基蒙脱土(钠土)分散于其中,制成复合乳胶涂层并涂覆在Q235钢上。研究了乳液种类和钠土用量对涂层防腐性的影响。采用红外光谱(FT-IR)、透射电子显微镜(TEM)和扫描电子显微镜(SEM)表征了氟硅丙烯酸酯乳液和涂层。通过极化曲线、交流阻抗测量和中性盐雾试验探讨了复合涂层的耐腐蚀性。结果表明,乳胶粒子呈核壳结构,涂层连续、致密,钠土在涂层中分散均匀。当钠土用量为4%时,复合涂层的耐蚀性最好,水接触角达到102.4°,附着力为0级,电化学阻抗达到104.4Ω,腐蚀速率仅为4.3×10-5 mm/a,盐雾试验240 h后膜下金属未发生腐蚀扩散。     

乳液法合成氯乙烯/乙烯基异丁醚共聚树脂

介绍了10L聚合釜乳液法氯乙烯/乙烯基异丁醚共聚树脂研制开发状况。讨论了pH值缓冲剂、聚合温度、引发体系、乳化剂等对合成氯醚树脂的影响规律。     

反应性乳化剂的制备及其在纯丙乳液聚合中的应用

将马来酸酐分别与苯甲醇、正辛醇、十二醇、十四醇和脂肪醇聚氧乙烯醚AEO-7通过酯化、中和反应生成相应的产物,依次记为ME-B,ME-8,ME-12,ME-14和M-AEO-7,测试并对比了各产物乳化力和临界胶束浓度的大小。结果表明ME-12和M-AEO-7的综合性能较佳。采用红外光谱对2者的结构进行表征。分别将十二烷基硫酸钠SDS、ME-12和M-AEO-7用于纯丙乳液聚合中,发现采用自制的反应性乳化剂所得乳液的聚合稳定性和乳胶膜的耐水性比SDS有所提高。将ME-12分别和AEO-3(AEO-5或AEO-7)以1∶1或1∶1.5质量比复配使用,仅在m∶m=1∶1.5时乳液的耐电解质稳定性才较好,而ME-12 AEO-7单独采用M-AEO-7即能得到耐电解质性能极佳的聚合物乳液。     

原位乳液聚合法制备改性蒙脱土及其表征

通过原位乳液聚合的方法制备改性蒙脱土,在聚合之前,可聚合的小分子先接枝到蒙脱土的表面或层间,然后加入苯乙烯单体引发聚合,使聚合物大分子接枝到蒙脱土的表面和层间。十六烷基三甲基溴化铵(CTAB)在乳液聚合改性蒙脱土的过程中既是插层剂又是乳化剂。X射线衍射分析表明,经过处理引入了CTA+和PS大分子使得层间距扩大;红外、热重法分析表明,小分子和大分子已接枝到蒙脱土上。蒙脱土的存在影响了聚合反应动力学,并就小分子的影响作了简单的讨论。     

Superabsorbent polymeric materials. XII. Effect of montmorillonite on water absorbency for poly(sodium acrylate) and montmorillonite nanocomposite superabsorbents

A series of novel xerogels based on sodium acrylate (NaA), montmorillonite (MMT), and N,N′‐methylene‐bisacrylamide (NMBA) were prepared by inverse suspension polymerization and water solution polymerization. The influences of pure MMT, intercalated MMT, the method of polymerization, and the content of the MMT in the copolymeric gels on the water absorbency and the initial absorption rate in deionized water and various salt solutions were investigated. Results showed that the water absorbency was increased by adding a small amount of the pure MMT into the copolymeric gels, but decreased by adding intercalated MMT into the gels. In addition, the water absorbency of the gels prepared by water solution polymerization was lower than that prepared by inverse suspension polymerization. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3422–3429, 2004     

Synthesis of poly(butyl acrylate‐co‐methyl methacrylate)/montmorillonite waterborne nanocomposite via semibatch emulsion polymerization

Poly(butyl acrylate‐co‐methyl methacrylate)‐montmorillonite (MMT) waterborne nanocomposites were successfully synthesized by semibatch emulsion polymerization. The syntheses of the nanocomposites were performed in presence of sodium montmorillonite (Na‐MMT) and organically modified montmorillonite (O‐MMT). O‐MMT was used directly after the modification of Na‐MMT with dimethyl dioctadecyl ammonium chloride. Both Na‐MMT and O‐MMT were sonified to obtain nanocomposites with 47 wt % solids and 3 wt % Na‐MMT or O‐MMT content. Average particle sizes of Na‐MMT nanocomposites were measured as 110–150 nm while O‐MMT nanocomposites were measured as 200–350 nm. Both Na‐MMT and O‐MMT increased thermal, mechanical, and barrier properties (water vapor and oxygen permeability) of the pristine copolymer explicitly. X‐ray diffraction and transmission electron microscope studies show that exfoliated morphology was obtained. The gloss values of O‐MMT nanocomposites were found to be higher than that of the pristine copolymer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42373.     

Preparation of UV-curable functionalized graphene/polyurethane acrylate nanocomposite with enhanced thermal and mechanical behaviors

Functionalized graphene nanosheets (f-GNSs) were synthesized by a simple covalent functionalization of graphene with 3-methacryloxypropyl trimethoxysilane (MPTES). The results from FTIR, XPS and XRD showed that MPTES was successfully attached onto the surface of graphene. Functionalized graphene/polyurethane acrylate (f-GNS/PUA) nanocomposites were prepared by UV radiation of PUA with f-GNS. The onset thermal degradation temperature of f-GNS/PUA nanocomposite was increased by 16 °C, at an f-GNS content of 1 wt%. Meanwhile, the storage modulus and glass transition temperature of the nanocomposites were enhanced by incorporating f-GNS into the PUA. This is believed to be attributed to that the covalent functionalization of graphene can improve both the dispersion of f-GNSs in the polymer matrix and the interfacial interactions between f-GNSs and PUA.     

甲基丙烯酸甲酯-丙烯酸乙酯乳液共聚动力学研究

为了合成适于药物包衣用的甲基丙烯酸甲酯-丙烯酸乙酯(MMA-EA)共聚物胶乳,对以非离子型乳化剂OP-10为乳化剂、过硫酸钾为引发剂的MMA-EA乳液共聚动力学进行了研究。发现初期共聚速率随着乳化剂浓度、引发剂浓度和聚合温度的增加而增大,这是由于共聚物乳胶粒子平均粒径随着乳化剂、引发剂浓度和聚合温度的增加而减小,乳胶粒子数目增加所致。通过调节乳化剂、引发剂以及反应温度可以达到合适的聚合反应速率,最终合成出转化率大于95%的MMA-EA共聚乳液。     

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     

Synthesis and self-assembly of poly(benzyl ether)-b-poly(methyl methacrylate) dendritic-linear polymers

Here, the dendritic chloric poly(benzyl ether) (G₁-Cl, G₂-Cl and G₃-Cl) as the macroinitiator for the controlled atom transfer radical polymerization (ATRP) of methyl methylacrylate was investigated. Polymers obtained were characterizated by GPC, ¹H NMR, FT-IR, TGA and DSC. These dendritic-linear block polymers that consist of linear and dendritic segments have very good solubility in common organic solvents at room temperature. In a selective solvent (THF/H₂O), polymers can self-assembled into the micelles that have a spherical morphology in shape due to the lowest of the surface energies.     

水性丙烯酸酯乳液的合成及性能研究

以双丙酮丙烯酰胺（DAAM）为功能性单体,采用预乳化半连续种子乳液聚合法合成水性丙烯酸酯乳液,添加己二酸二酰肼（ADH）为交联剂,构成室温自交联体系。考察了DAAM、ADH用量对乳液及其乳胶膜性能的影响。用傅里叶红外光谱仪（FT-IR）对交联反应进行了表征。通过差示扫描量热法、力学性能和耐溶剂性能的测试等方法研究了乳液和乳胶膜的性能。结果表明,当DAAM用量为2.4%~3.5%,ADH与DAAM的当量比为1~1.2时,乳液和乳胶膜的综合性能较好。