细乳液聚合制备纳米SiO2／含氟丙烯酸酯复合乳液及其性能研究

采用溶胶-凝胶法,以正硅酸乙酯为前驱物,在丙烯酸酯单体为油相介质中原位生成纳米SiO2粒子,并通过细乳液聚合,制备出纳米Si02／含氟丙烯酸酯复合乳液。研究了含氟单体和SiO2的用量对复合乳胶膜性能的影响,并采用FT-IR,DSL等分析手段对产物进行了表征。结果表明：该乳液具有良好的稳定性,粒径分布较窄。当（甲基丙烯酸十二氟庚酯）FA与SiO2的用量分别为6％和5．5％时,乳胶膜表现出良好的疏水性能,对水的接触角达到了102．7°,吸水性降低到6．9％。     

纳米SiO_2改性氟硅丙烯酸酯共聚物的性能研究

文章采用乳液聚合的方式,用纳米Si O2改性甲基丙烯酰氧乙基三甲氧基硅烷(KH-570)后,与含氟聚合物聚合,制备了氟硅丙烯酸酯聚合物。研究结果表明,加入纳米Si O2之后,聚合物的分子排列规整,结晶度提高;涂膜致密程度较高,表面粗糙度增加;乳胶膜对水接触角111°。     

纳米TiO2-有机氟-丙烯酸酯涂料乳胶的制备及性能

以改性纳米 TiO₂、甲基丙烯酸甲酯（ MMA）、丙烯酸甲酯（MA）、丙烯酸正丁酯（ BA）和甲基丙烯酸十二氟庚酯（ G04）为原料,通过乳液聚合法制备了 TiO₂-有机氟 -聚丙烯酸酯复合乳胶。研究了纳米 TiO₂和 G04的添加对复合乳胶膜性能的影响。结果表明：乳胶平均粒径约为 88. 54 nm,具有良好的抗紫外性能。 XPS和 EDS分析表明：含 F链段会向胶膜 -空气的表面迁移,且大量富集在膜外空气界面。当 G04含量为 20%时,胶膜的吸水率为 10. 21%,水接触角为 124. 21°,相比纯丙乳胶膜,其疏水性大幅提高。且乳胶膜具有良好的耐热稳定性、抑制黑曲霉菌等性能,复合乳胶可以在基材表面形成疏水抑菌防霉的防护膜。相比于含氟聚丙烯酸酯,纳米 TiO₂的添加进一步改善了复合乳胶膜的耐磨性和抗污性等应用性能。     

核壳型含氟丙烯酸酯共聚乳液

以十二烷基硫酸钠（SDS）和壬基酚聚氧乙烯基醚（OP-10）为复合乳化剂，甲基丙烯酸十二氟庚酯（Actyflon-God）、甲基丙烯酸甲酯（MMA）、丙烯酸丁酯（BA）为原料制备了壳层含氟的核壳型丙烯酸酯共聚物乳液。用红外光谱（FT—IR）表征乳胶膜化学组成，用透射电子显微镜（TEM）观察了乳胶粒的微观形态结构，并用X射线光电子能谱（XPS）进行了表面分析。发现氟有向空气与膜面迁徙的现象。通过吸水率表征含氟丙烯酸酯共聚物乳胶膜的表面性能，结果表明含氟量增加使乳胶膜吸水率大大降低。     

有机氟无机纳米二氧化钛复合改性丙烯酸酯乳液的制备及性能研究

采用半连续种子乳液法将自制的表面亲油性接枝改性纳米二氧化钛与含氟单体甲基丙烯酸十三氟辛酯(G06B)等复合改性丙烯酸酯乳液,用红外光谱(FT-IR)、乳胶膜表面形态分析(AFM)、热重(TG)和拉力机等测试手段研究了表面改性无机纳米TiO_2以及有机氟的引入对乳液及乳胶膜性能的影响。结果表明,改性TiO_2的引入显著增强了聚合物乳胶膜的力学性能并进一步优化了乳胶膜的表面疏水性;乳胶膜疏水性随含氟单体用量增加而增大,热稳定性也有一定地提高,当G06B用量为20%、改性TiO_2用量为0.2%时,乳胶膜的综合性能相对最佳。     

阳/非离子乳化剂制备氟改性丙烯酸酯乳液

采用阳离子和非离子乳化剂相复配的乳化体系，以甲基丙烯酸甲酯（MMA）、丙烯酸丁酯（BA）、甲基丙烯酸十二氟庚酯（FMA）等作为单体，通过半连续法制备了丙烯酸酯共聚物乳液。研究了不同乳化剂的配比对聚合稳定性和乳液的钙离子稳定性的影响，通过吸水率和接触角的测定研究了氪单体的用量对乳胶膜耐水性能的影响，并用透射电子显微镜（TEM）观察了乳胶粒子的形态。结果表明，采用非／阳离子乳化剂质量比为2．5：1的复合乳化体系，可制备出稳定的含氟丙烯酸酯共聚物乳液；添加一定量的氟单体对体系进行改性，能使乳胶膜的表面能和吸水率降低、对水的接触角增大。     

一种新型复合医用乳胶膜的制备及其生物学性能研究

将纳米羟基磷灰石与天然胶乳复合,制备出羟基磷灰石/天然胶乳复合医用乳胶膜。采用广角X射线衍射（XRD）和透射电子显微镜（TEM）对纳米羟基磷灰石进行表征,结果表明与人体内羟基磷灰石纳米晶非常相似。对羟基磷灰石/天然胶乳复合医用乳胶膜的力学性能、蛋白质含量以及生物相容性进行的测试表明这是一种非常有前途的医用复合材料,有望获得广泛应用。     

SiO2／聚丙烯酸酯复合乳液的制备和表征

通过半连续种子乳液聚合法．在Si02溶胶存在情况下,利用有机硅单体乙烯基三乙氧基硅烷（A-151）的桥接作用,制备得到Si02／丙烯酸酯共聚物杂化乳液。对有机硅单体和二氧化硅用景对复合乳液稳定性能的影响进行了研究,采用投射电镜（TEM）和热重分析（TGA）对制备得到的复合乳液的形貌和耐热性进行测试表征。结果表明：在有机硅单体乙烯基三乙氧基硅烷用量为总单体4．0wt％,SiO2溶胶用鲢为单体15wt％以内,可制备出稳定的SiO2／丙烯酸酯共聚物杂化乳液。由于有机硅单体的桥接作用,部分SiO2粒子形成与乳胶粒上,形成草莓状的复合结构,且复合乳液其有较高的耐热性。     

纳米TiO_2-有机氟-聚丙烯酸酯乳胶的制备及性能研究

以改性纳米TiO_2、甲基丙烯酸甲酯(MMA)、丙烯酸甲酯(MA)、丙烯酸正丁酯(BA)和甲基丙烯酸十二氟庚酯(G04)为原料,通过乳液聚合法制备了TiO_2-有机氟-聚丙烯酸酯复合乳胶。研究了纳米TiO_2和G04的添加对复合乳胶膜性能的影响。结果表明:乳胶平均粒径约为88.54 nm,具有良好的抗紫外性能。XPS和EDS分析表明:含F链段会向胶膜-空气的表面迁移,且大量富集在膜外空气界面。当G04含量为20%时,胶膜的吸水率为10.21%,水接触角为124.21°,相比纯丙乳胶膜,其疏水性大幅提高。且乳胶膜具有良好的耐热稳定性、抑制黑曲霉菌等性能,复合乳胶可以在基材表面形成疏水抑菌防霉的防护膜。相比于含氟聚丙烯酸酯,纳米TiO_2的添加进一步改善了复合乳胶膜的耐磨性和抗污性等应用性能。     

纳米羟基磷灰石/天然胶乳复合乳胶膜的制备及性能表征

对比研究了纳米羟基磷灰石(n-HA)经硅烷偶联剂(KH-570)表面改性前后的性能变化,实验结果表明,n-HA经改性后,疏水性得到提高,其表面与KH-570发生了偶联作用(FT-IR);将改性的n-HA与天然胶乳复合制备复合乳胶膜,力学性能测定结果表明,复合乳胶膜的力学强度与未经处理的相比有一定提高;另外n-HA还能够有效的抑制复合乳胶膜中水溶性蛋白的析出,利用考马斯亮蓝法测定复合材料中的水溶性蛋白,随着n-HA的添加量的增加,复合乳胶膜中的水溶性蛋白被屏蔽,溶出量逐渐降低。     

纳米SiO2对丙烯酸罩光漆耐磨性的改性研究

经偶联剂表面处理的纳米SiO2,通过超声分散和离心处理后均匀分散在丙烯酸罩光漆中,制得了丙烯酸/纳米SiO2复合罩光漆。对该罩光漆漆膜耐磨性、附着力、磨损行为等进行了研究。研究结果表明:纳米SiO2对漆膜的摩擦行为及耐磨性等产生较大的影响,当纳米SiO2添加量为3.0%时,丙烯酸/纳米SiO2复合罩光漆漆膜的耐磨性可提高48.7%,漆膜的附着力、柔韧性、抗冲击强度等性能也得到明显改善。     

Synthesis and characterization of polyacrylate latex containing fluorine and silicon via semi-continuous seeded emulsion polymerization

The polyacrylate latex containing fluorine and silicon were successfully synthesized by semi-continuous seeded emulsion polymerization in the presence of the mixed emulsifier of novel sodium lauroyl glutamate (SLG) anion surfactant and BCE-10 nonionic surfactant, which methyl methacrylate (MMA) and butyl acrylate (BA) were used as main monomers and hexafluorobutyl methacrylate (HFMA) and vinyltriethoxysilane (VTES) were used as the functional monomers. Potassium persulfate (KPS) was used as the initiator. The structural groups of the latex films were evaluated by Fourier transform infrared spectroscopy (FTIR). Thermal performance of the film was evaluated by differential scanning calorimetry (DSC) and thermogravimetric analysis. The latex particle size and its distribution were measured by the dynamic light scattering detector. Furthermore, surface hydrophobicity of the latex film was examined by measurement of water contact angle (WCA). WCA and thermal stability of the film are increased with the increased amount of HFMA and VTES. Factors, which have an influence on the properties of the resultant latex and its film, are investigated in detail. Results show that the optimal condition of synthesizing the emulsion is as follows: the amount of emulsifiers is 7.0%; mass ratio of SLG to BCE-10 is 1:1; the amount of initiator is 0.8%; the mass ratio of MMA to BA is 1:1; the content of the fluorine monomer and silicon monomer is 6.0%.     

纳米SiO_2改性苯丙乳液乳胶漆的研究

通过硅烷偶联剂改性纳米SiO2与丙烯酸丁酯、苯乙烯、甲基丙烯酸3种单体共聚,合成纳米SiO2/苯丙乳液,以其作为主要成膜物制得了乳胶漆。测试了纳米SiO2粒子改性后的微观结构,讨论纳米SiO2含量对乳胶漆的耐老化性、耐洗刷性、耐水性等的影响。     

Synthesis and characterization of fluorine-containing poly-styrene-acrylate latex with core–shell structure using a reactive surfactant

Fluorine-containing poly-styrene-acrylate (PSA) latex with core–shell structure was successfully synthesized by seeded semicontinuous emulsion polymerization using fluorine monomer Actyflon-G₀₄ and reactive emulsifier DNS-86. The chemical composition, morphology of latex, and surface composition of the latex film were characterized by Fourier transform infrared spectra, transmission electron microscopy, and X-ray photoelectron spectroscopy, respectively. The stability properties of latex were tested by Ca²⁺, centrifugal and mechanical stability tests, and the latex film was studied by water contact angle, water absorption ratio, and thermo-gravimetric analysis. The results show that fluorine-containing PSA latex particles with crosslinked core and crosslinked shell structure have excellent stability properties, and the film of latex has excellent water repellency, thermal stability, and chemical resistance properties when the amount of fluorine monomer was only 8.0 wt%.     

纳米SiO2/聚氨酯-含氟丙烯酸酯杂化乳液的合成与表征

采用种子乳液聚合法,以聚氨酯（PU）乳液为种子（在聚合过程中为壳相）,甲基丙烯酸甲酯（MMA）、丙烯酸丁酯（BA）、甲基丙烯酸十二氟庚酯（DFMA）和γ-甲基丙烯酰氧丙基三甲氧基硅烷（KH-570）改性的纳米SiO₂组成的混合物为核相,合成了具有核壳结构的纳米SiO₂/聚氨酯-含氟丙烯酸酯（SiO₂/FPUA）复合乳液。考察了纳米SiO₂和DFMA用量对乳液聚合过程及乳胶膜性能的影响。通过傅里叶红外光谱（FT-IR）、接触角（CA）、透射电子显微镜（TEM）、热重（TG）、差示扫描量热仪（DSC）和力学性能测试（MPT）等表征乳液的结构形态、乳胶膜的表面性能和综合性能。结果表明：乳胶粒子呈现“反相核壳”结构,以聚丙烯酸酯（PA）相为核,PU相为壳;由于纳米SiO₂和DFMA的协同作用,涂膜的疏水性和综合性能得到了较大的提高。     

甲基丙烯酸接枝环氧树脂的制备与性能测试

通过丙烯酸类单体与环氧树脂接枝共聚反应,在环氧树脂中引入强亲水性基团-COOH,制备水性环氧乳液。探索了不同单体用量和加水温度对所得水性乳液的pH值、黏度、粒径、水分散性和储存稳定性的影响;考察了涂膜固化条件对涂膜的附着力、耐冲击性、耐水性的影响。试验结果表明,随着甲基丙烯酸用量增加,所制备的水性环氧乳液水分散稳定性增强,pH值降低,粒径变小;随着加水温度的增加,储存稳定性变差;固化剂含量占环氧树脂含量的15%和固化温度为120℃时,涂膜的外观、附着力、耐冲击性、耐水性等综合性能最好。     

含巯基有机硅改性水性苯丙乳液的制备及性能

以丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)、苯乙烯(St)和丙烯酸(AA)为反应单体,利用羟基硅油(SO)与3?巯丙基甲基二甲氧基硅烷(MPDMS)制备的含巯基有机硅(PMMS)为改性剂,通过种子乳液聚合的方法,制备了一系列有机硅改性水性苯丙复合乳液.通过红外光谱(FTIR)、核磁共振(NMR)和凝胶渗透色谱(GP...     

核壳型聚丙烯酸酯乳液的耐水性能研究

采用种子乳液二阶段聚合法,制备了经丙烯酸(AA)/丙烯酰胺(AM)交联、具有核壳结构的甲基丙烯酸甲酯(MMA)/丙烯酸丁酯(BA)/丙烯腈(AN)复合乳液,研究了核壳软硬单体比、AN及壳层中交联单体AM含量对乳胶膜吸水率的影响。结果表明:乳胶膜吸水率主要受壳层软硬单体比例的影响,软硬单体比值越小,乳胶膜的吸水率越低;丙烯酸/丙烯酰胺复合交联剂对乳胶膜吸水率的影响不明显;功能单体丙烯腈可明显降低乳胶膜的吸水率,乳胶膜吸水率随丙烯腈含量的增加而逐渐降低,最低达到9.40%。     

Fabrication and properties of polysilsesquioxane-based trilayer core–shell structure latex coatings with fluorinated polyacrylate and silica nanocomposite as the shell layer

Polysilsesquioxanes (PSQ)-based core–shell fluorinated polyacrylate/silica hybrid latex coatings were synthesized with PSQ latex particles as the seeds, and methyl methacrylate, butyl acrylate, 3-(trimethoxysilyl) propyl methacrylate (MPS)-modified SiO₂ nanoparticles (NPs), 1H,1H,2H,2H-perfluorooctyl methacrylate (PFOMA) as the shell monomers by emulsifier-free miniemulsion polymerization. The results of Fourier transform IR spectroscopy, transmission electron microscopy, and dynamic light scattering suggested the obtained hybrid particles emerged with trilayer core–shell pattern. Contact angle analysis, x-ray photoelectron spectroscopy, and atom force microscopy results indicated that the hybrid film containing SiO₂ NPs showed higher hydrophobicity, lower surface free energy and water absorption, in comparison with the control system (without SiO₂ NPs). Compared with the control system, the hybrid latex film containing SiO₂ NPs in the fluorinated polyacrylate shell layer showed the higher content of fluorine atoms and a rougher morphology on the film surface. Additionally, thermogravimetric analysis demonstrated the enhanced thermostability of PSQ-based nanosilica composite fluorinated polyacrylate latex film.     

Preparation and surface properties of core‐shell polyacrylate latex containing fluorine and silicon in the shell

The core‐shell polyacrylate latex particles containing fluorine and silicon in the shell were successfully synthesized by a seed emulsion polymerization, using methyl methacrylate (MMA) and butyl acrylate (BA) as main monomers, dodecafluoroheptyl methacrylate (DFMA), and γ‐(methacryloxy) propyltrimethoxy silane (KH‐570) as functional monomers. The influence of the amount of fluorine and silicon monomers on the emulsion polymerization process and the surface properties of the latex films were discussed, and the surface free energy of latex films were estimated using two different theoretical models. The emulsion and its films were characterized by particle size distribution (PSD) analysis, transmission electron microscopy (TEM), Fourier transform infrared spectrum (FTIR), nuclear magnetic resonance (¹H‐NMR and ¹⁹F‐NMR) spectrometry, contact angle (CA) and X‐ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), and thermogravimetry (TG) analysis. The results indicate that the average particle size of the latex particles is about 160 nm and the PSD is narrow, the synthesized latex particles exist with core‐shell structure, and a gradient distribution of fluorine and silicon exist in the latex films. In addition, both the hydrophobicity and thermal stability of the latex films are greatly improved because of the enrichment of fluorine and silicon at the film‐air interface, and the surface free energy is as low as 15.4 mN/m, which is comparable to that of polytetrafluoroethylene (PTFE). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011