含氟丙烯酸酯共聚乳液的制备及表征

以甲基丙烯酸甲酯（MMA）、丙烯酸丁酯（BA）等为主要单体,丙烯酸全氟烷基酯（Zonyl TM）为含氟单体,甲基丙烯酸羟乙酯（HEMA）为交联单体,采用种子乳液聚合法制备了含氟丙烯酸酯共聚物乳液。研究了Zonyl TM、HEMA、引发齐（APS）用量、复合乳化剂（SDS/OP—10）、聚合温度、聚合时间和搅拌速度等因素对聚合反应最终转化率、耐水性和乳液稳定性的影响。制备的乳液单体总转化率高,乳液凝聚率低,聚合反应稳定,涂膜的综合性能优良。此外,含氟乳胶膜对水的接触角及TG分析结果表明,Zonyl TM有效参与了共聚反应,提高了涂膜的耐水性及耐热性。     

自交联含氟丙烯酸酯乳液的合成与性能研究

以甲基丙烯酸十二氟庚酯(DFHMA)为含氟丙烯酸酯单体,甲基丙烯酸酯衍生物(HA)为交联单体,烯丙氧基壬基酚聚氧乙烯(10),醚单磷酸(ANPEO10-P1)为乳化剂,采用预乳化、半连续法聚合方式,合成了自交联含氟丙烯酸酯乳液.研究了HA和DFHMA的用量对乳胶粒子粒径及其分布和乳胶膜硬度、吸水性、对水接触角等性能的影响.结果表明:当HA用量为4%(wt),DFHMA用量为8%(wt)时,得到的乳液粒径小,分布窄,稳定性好,乳胶膜表现出良好的疏水性能,对水的接触角达到了97.5°.     

含氟丙烯酸酯核壳乳液的制备与性能研究

以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)为主单体,分别加入丙烯酸六氟丁酯(HFBMA)和甲基丙烯酸十二氟庚酯(DFHM)作为聚丙烯酸酯改性剂,制备了2种含氟丙烯酸酯核壳乳液。采用1H-NMR、TEM、DSC、EDS-SEM、Zeta电位及纳米激光粒度仪等表征了乳胶粒子的组成、结构、粒径及其分布以及乳胶膜表面氟元素的含量。研究了2种含氟单体的用量对乳液稳定性、乳胶膜吸水率、单体转化率、乳胶膜表面疏水疏油性等的影响;研究结果表明:DFHM的改性效果明显好于HFBMA。当DFHM的加入量为4%时,乳胶膜对水的接触角达到93.5°,吸水率降为11.54%,对正己烷的接触角达到82.0°;乳胶粒子的平均粒径70.02 nm,粒径分布窄(PDI=0.082),且具有核壳结构;SEM-EDS测试结果显示,制备的含氟聚合物在成膜过程中,氟元素更易向表面迁移,从理论的5.70%上升到13.47%,从而使乳胶膜具有更好的疏水和疏油性能。     

丙烯酸酯后交联乳液的性能研究

以MMA(甲基丙烯酸甲酯)和BA(丙烯酸丁酯)为主单体,HEMA(甲基丙烯酸羟乙酯)为交联单体制备了丙烯酸酯后交联乳液,探讨了HEMA用量对乳液单体转化率、聚合速率、粒径及其分布、凝胶率以及交联前后乳胶膜交联度、水接触角、力学性能和耐热性的影响。研究结果表明:HEMA明显影响,但对聚合稳定性有促进作用;当其含量超过3%乳液粒径分布变宽,进一步增加则会导致粒径增加;同时,HEMA显交联,交联后乳胶膜交联度可达80%显提高。     

含氟丙烯酸酯改性聚氨酯核壳乳液的制备及表征

以双键封端水性聚氨酯为反应型高分子,全氟丁基磺酸钾为含氟乳化剂,实现甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、甲基丙烯酸十二氟庚酯(G04)和聚氨酯的共聚,制备具有核壳结构的含氟丙烯酸酯改性聚氨酯乳液(FPUA)。傅里叶变换红外光谱(FTIR)和透射电子显微镜(TEM)对共聚物组成、乳胶粒的形态进行表征,并通过表面接触角、拉伸实验和热重分析等分别研究了FPUA胶膜的表面能、力学性能和热性能。结果表明,当含氟乳化剂和氟单体用量分别为单体总质量的0.15%和20%时,乳液稳定性好,聚合物胶膜表面能由45.6mN/m下降至22.5 mN/m,表现出良好的疏水疏油性,最大热失重速率温度由348℃提高至398℃。     

硅丙乳液聚合过程稳定性影响研究

为了考察硅丙乳液聚合过程稳定性的影响因素,对硅丙乳液进行配方设计,考察了有机硅单体的用量、滴加方式、种类、反应温度等对乳液聚合过程及乳液稳定性的影响。测试结果表明:有机硅单体用量为5%时,乳液聚合稳定性和乳胶膜耐水白性达到平衡,平均凝胶率为0.09%;采用核壳结合滴加方式,乳液聚合稳定性最佳;使用有机硅单体A-174所得乳液平均凝胶率最小;当反应温度为80℃时,单体平均转化率和聚合稳定性达到平衡。     

有机硅改性丙烯酸酯乳液的制备及表征

以γ-甲基丙烯酰氧丙基三甲氧基硅烷(KH-570)、八甲基环四硅氧烷(D4)、丙烯酸酯类单体为原料,制备了有机硅改性丙烯酸酯乳液.考察了乳化剂配比、有机硅用量对乳液及乳胶膜性能的影响,并用红外光谱、凝胶渗透色谱、透射电镜进行了表征.结果表明KH-570先与低聚体D4开环预聚,再与丙烯酸酯类单体进行自由基聚合,可得到有机硅改性丙烯酸酯乳液;当有机硅占单体总质量的9%,其中m(KH-570)∶m(D4)=1∶9,m(MS-1)∶m(AEO)=2∶1时,乳液的黏度、凝胶率和乳胶膜的硬度随有机硅用量的增加而增大,乳胶膜的吸水率则降低;乳胶粒表面光滑均一,呈规则的圆球状,平均粒径为100 nm,其重均摩尔质量Mw=1.75×104g/mol,摩尔质量分布Mw/Mn=1.3.     

含氟丙烯酸酯共聚物无皂乳液的粒子形态与性能研究

研究了通过半连续滴加法制备的无皂含氟丙烯酸酯聚合物乳液乳胶粒形态、聚合条件对乳胶粒粒径的影响,测定了乳液性能和乳胶膜的表面性能。制备的含氟乳液的乳胶粒呈圆形,粒径分布窄。乳液稳定性好,含氟乳胶膜对水的接触角为110.2°,吸水率低,表现出优异的表面性能。     

微波辐射制备室温自交联含氟聚丙烯酸酯乳液

在微波辐射下,以甲基丙烯酸十二氟庚酯(DAAM)为含氟单体,双丙酮丙烯酰胺为功能单体,己二酸二酰肼为交联剂,阴离子十二烷基硫酸钠和非离子脂肪醇聚氧乙烯醚为复合乳化剂,在过硫酸钾的引发下,制备了可室温自交联的含氟聚丙烯酸酯乳液。考察了交联单体用量对转化率、粒径分布及分布指数和乳胶膜吸水率的影响。w(DAAM)为5%时,乳液乳胶粒呈球形,平均粒径在60~70 nm。随着DAAM用量的增加,乳胶膜吸水率减小,此时交联起主导作用;进一步增加DAAM用量,乳胶膜吸水率反而增大,此时亲水性起主导作用。     

细乳液聚合法制备含氟丙烯酸酯共聚物乳液的研究

通过细乳液聚合法制备含氟丙烯酸酯共聚物（FPA）乳液,采用红外光谱（ FT-IR）、透射电镜（TEM）、原子力显微镜（AFM）、热重分析仪（ TG）、扫描电镜和表面能谱（ SEM-EDS）等对聚合物进行表征,并考察了乳化剂与助乳化剂的物质的量比,氟单体用量和超声时间对乳液粒径的影响。结果表明,甲基丙烯酸六氟丁酯（ 6FA）、丙烯酸丁酯（ BA）、苯乙烯（ St）3种单体成功聚合,乳化剂与助乳化剂的物质的量比为 1.5∶1,超声时间为 60 min,氟单体用量为 10%时,乳液粒径最小且分布较窄,表面张力从 45.028 mN/m降至 33.399 mN/m,且乳胶膜粗糙度增加,热稳定性提高。     

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%.     

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.     

丙烯酰胺改性丙烯酸酯乳液的合成及性能研究

通过预乳化半连续法制备了丙烯酰胺(AM)改性的丙烯酸酯乳液,探讨了功能单体AM用量对丙烯酸酯乳液和乳液胶膜性能的影响。结果表明:当AM用量为单体质量的1.0%时,乳液及乳液胶膜的综合性能最好。此时,功能单体AM改性的丙烯酸酯乳液聚合稳定性和转化率有所提高;乳液胶膜的力学性能有较大幅度的提高,吸水率有一定程度的降低。     

Role of acrylic acid in the synthesis of core‐shell fluorine‐containing polyacrylate latex with spherical and plum blossom‐like morphology

The core‐shell fluorine‐containing polyacrylate latex was successfully synthesized by two‐stage semicontinuous emulsion copolymerization of methyl methacrylate (MMA), butylacrylate (BA), acrylic acid (AA), and dodecafluoroheptyl methacrylate (DFMA). The fluorine‐containing polyacrylate latex was characterized by Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), dynamic light scattering (DLS), zeta potential, thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC). The effects of AA content on monomer conversion, polymerization stability, particle size, corsslinking degree, carboxyl groups distributions (latex surface, aqueous phase or buried in latex), as well as mechanical properties and water absorption rate of latex film were investigated. The obtained fluorine‐containing polyacrylate latex exhibited core‐shell structure with a particle size of 120–150 nm. The introduction of AA was beneficial for the increase of monomer conversion and the polymerization stability, and had little effects on the mechanical property of latex film. However, the hydrophilicity of AA made the water resistance of latex film get bad. With the increase of AA content, the carboxyl groups preferred to distribute on aqueous phase, and the possibility of homogeneous nucleation increased and more oligomers particles were formed. Moreover, the oligomers would distribute to the latex and continued to grow up, making the latex morphology changed from spherical to plum blossom‐like. The core‐shell latex had two T_g corresponding to the rubber polyacrylate core and hard fluorine‐containing polyacrylate shell, and the latex film possessed excellent thermal stability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42527.     

Preparation and Characterization of Soap-free Cationic Fluorinated Poly-styrene-acrylate Latex with Core-shell Structure

Soap-free cationic fluorinated Poly-styrene-acrylate latex particles with core-shell structure were synthesized by seeded semi-continues emulsion polymerization in the presence of water soluble cationic monomer Methacryloxyethyltrimethyl ammonium chloride (MADAC) and using ethanol as co-solvent. The effects of MADAC dosage and ethanol content on the stability of polymerization process and the properties of the latex particles were studied. The chemical component of the polymer was analyzed by Fourier transform infrared (FTIR). The surface element composition of the prepared copolymer film was analyzed by X-ray photoelectron spectroscopy (XPS), the micro-structure of the prepared latex particles were observed by transmission electron microscopy (TEM). The result shows that cationic soap-free fluorinated poly-styrene-acrylate emulsion with a core-shell structure can be prepared when monomer DAMAC is 6.0 wt% and ethanol is 7.5 wt%.     

含胺基水溶性单体的乳液共聚合研究

制备了含水溶性单体甲基丙烯酸二甲氨基乙酯(DM)的三元共聚物乳液。研究了聚合工艺、DM含量对聚合的影响。结果表明少量DM参与共聚不但不会影响乳液的稳定性,还可提高聚合反应速率;但是,当DM含量5%时,随着DM含量的增加,乳胶粒聚并加剧,稳定性降低。当DM含量超过10%时,三元共聚物可以在酸性介质中溶解。     

POSS/有机硅改性聚丙烯酸酯无氟防水剂的合成与应用研究

通过无皂乳液聚合技术合成了POSS/有机硅改性聚丙烯酸酯无氟防水剂,并将其应用于棉织物整理。考察了软硬单体配比对乳液、乳胶膜及其应用性能的影响。利用傅里叶红外光谱(FT-IR)和傅里叶红外光谱(DLS)对聚丙烯酸酯的结构及乳胶粒的粒径大小进行了表征,利用伺服材料多功能高低温控制试验机、柔软度仪、SEM对整理织物的应用性能及表面形貌进行了表征。结果表明：当m(BA):m(MMA)为6:4时,单体的转化率最大为96.97%,乳液的凝胶率为0.14%,乳胶粒的粒径最小为104.8 nm,乳胶膜对水的接触角最大可达114.3?,并具有优异的耐水性。整理棉织物表现出优异的力学性能和良好的柔软度,其对水的接触角可达161?。SEM结果表明棉织物纤维表面存在功能化POSS纳米颗粒。无氟防水剂赋予棉织物纤维表面低的的表面能和一定的粗糙结构,从而使整理棉织物表现出超疏水性能。     

水解对乙烯－乙酸乙烯共聚物乳液复合的影响Ⅲ.复合乳液的性能

对水解处理后的乙烯－乙酸乙烯共聚物（ＥＶＡ）乳液与丙烯酸丁酯、甲基丙烯酸丁酯的复合乳液的性能进行了表征。结果表明,复合单体的水解处理后的ＥＶＡ乳胶粒表面的接枝状况对复合乳液的稳定性及其胶膜的而水性和力学性能有较大影响,热处理对胶膜性能的影响与复合单体的ＥＶＡ乳胶粒表面的接枝状况有关。     

Synthesis and properties of branched organosilicon-acrylate copolymer latexes

Summary Stable organosilicon-acrylate copolymer latexes with high silicon content were prepared by seeded semibatch emulsion polymerization of butyl acrylate (BA), methyl methacrylate (MMA) with a novel branched organosilicon monomer 3-methacryloxypropyl tris(trimethylsiloxy) silane (MPTS). Monomer conversion, evolution of the particle size and its distribution were monitored by dynamic light scattering. The effects of MPTS on the polymerization kinetics, the nucleation mechanism and properties of latex were investigated. The results indicated that, in addition to micellar nucleation, a coagulative nucleation step was also observed as a result of the addition of the organosilicon monomer, accordingly, the particle number of the silicon-acrylate latexes increased, the average particle diameter decreased and the polymerization rate accordingly increased compared to those of the acrylate latexes without organosilicon monomer. Moreover, the particle size distribution presented bimodal curves, which indicated that there were large particles formed at an early stage. However, the particle size distribution curves became monomodal at the later stage, and the final latex shows a narrow particle size distribution. It was found that the properties of latex and latex film were obviously influenced by MPTS content. With increasing MPTS content, latex film glass transition temperature and water absorption ratio decreased, the degradation temperature and water contact angle were increased. Hence, the resulting latex films containing MPTS showed lower glass transition temperature and excellent water-resistance, which probably due to the incorporation of the bulky branched hydrophobic group of MPTS into the copolymer chains.     

Study on the preparation and properties of styrene–butyl acrylate–silicone copolymer latices

Copolymer latices of styrene–butyl acrylate–silicone were prepared using a semicontinuous addition process and batch and monomer emulsion addition processes. The results showed that a stable latex with narrow particle size dispersion and a high monomer conversion can be obtained only by the semicontinuous addition process. The simultaneous free‐radical and ionic copolymerization mechanisms were discussed. 3‐Methacryloyloxypropyl trimethoxysilane in this work was used as a coupling agent to form a chemical bond between vinyl polymer and polysiloxane. It was found that the copolymerization reaction and the properties of latex and latex film were obviously influenced by silicone content. When the silicone content was less than 25 wt %, copolymerization proceeded readily and a stable latex could be prepared. With increasing silicone content, monomer conversion, latex stability, film hardness, and tensile strength decreased, whereas the water resistance and impact strength increased. Results of Soxhlet extraction, silicon analysis, and dynamic mechanical properties of latex polymer confirmed the occurrence of copolymerization. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3194–3200, 2001