Morphologies and dynamic mechanical properties of core‐shell emulsifier‐free latexes and their copolymers for P(BA/MMA)/P(MMA/BA) and P(BA/MMA)/PSt systems in the presence of AHPS

Different poly(methyl methacrylate/n‐butyl acrylate)/poly(n‐butyl acrylate/methyl methacrylate) [P(BA/MMA)/P(MMA/BA)] and poly(n‐butyl acrylate/methyl methacrylate)/polystyrene [P(BA/MMA)/PSt] core‐shell structured latexes were prepared by emulsifier‐free emulsion polymerization in the presence of hydrophilic monomer 3‐allyloxy‐2‐hydroxyl‐propanesulfonic salt (AHPS). The particle morphologies of the final latexes and dynamic mechanical properties of the copolymers from final latexes were investigated in detail. With the addition of AHPS, a latex of stable and high‐solid content (60 wt %) was prepared. The diameters of the latex particles are ～0.26 μm for the P(BA/MMA)/P(MMA/BA) system and 0.22–0.24 μm for the P(BA/MMA)/PSt system. All copolymers from the final latexes are two‐phase structure polymers, shown as two glass transition temperatures (T_gs) on dynamic mechanical analysis spectra. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3078–3084, 2002     

Preparation of high solids stable translucent nanolatexes of MMA/BA copolymers and MMA/BA/Veova-10 terpolymers with low MFFT using green industrial surfactants

In this study, high solids (∼40 wt%) stable translucent nanolatexes of MMA/BA copolymers and MMA/BA/Veova-10 terpolymers with MFFT ≤ 0 °C were synthesized by a modified semi-continuous microemulsion copolymerization. Ammonium persulfate was used as initiator and a redox system for post-polymerization to reduce the free monomers and achieve over 99.9% conversion. Methacrylic acid or acrylic acid at 1 wt% (calculated on monomers) and a combination of various “green” industrial anionic and non-ionic surfactants free of alkylphenol ethoxylates (APEO-free) at low concentrations (up to 10 wt% on monomers) were used. The resulting latexes were composed of polymer nanoparticles with average diameter size 50–80 nm and low polydispersity index. These friendly to the environment latexes can be potentially used as impregnation primer instead of classic solvent acrylic primers in architectural coatings.     

自交联封闭性乳液的合成与性能

以双丙酮丙烯酰胺（DAAM）、甲基丙烯酸甲酯（MMA）、丙烯酸丁酯（BA）和甲基丙烯酸（MAA）为共聚单体,采用半连续种子乳液聚合工艺合成自交联封闭性聚丙烯酸酯乳液（PAE）,考察了DAAM和复合乳化剂对乳液聚合稳定性以及涂膜性能的影响。研究发现：随着DAAM含量的增加,乳液聚合稳定性下降,粒径增大,涂膜的耐介质性能和交联度提高,合适的DAAM加入量为总单体质量的3.0%,DAAM和己二酰肼(ADH)的最佳摩尔比为2∶1。采用SDBS+OP-10+OP-40为复合乳化剂体系,选用乳化剂的含量为2.35%,阴/非离子乳化剂质量比为1∶1.25;复合乳化剂在种子、核、壳比例为1.5∶1∶2,制备的乳液具有较好的聚合稳定性（乳液凝胶率低和单体转化率高）,乳液耐电解质（钙离子）稳定性好,涂膜具有优异的封闭性。傅里叶红外光谱（FTIR）表明在涂膜形成过程中DAAM的酮羰基与ADH的酰肼基反应生成腙（C=N）,TEM分析显示乳液的乳胶粒子呈核壳结构,TGA分析发现DAAM改性的PAE降低了涂膜的热稳定性。     

乙烯基硅橡胶为助乳化剂的MMA/BA细乳液共聚合--水溶性引发体系

以十二烷基硫酸钠为乳化剂，乙烯基硅橡胶为助乳化剂、过硫酸铵为引发剂，研究了甲基丙烯酸甲酯和丙烯酸丁酯的细乳液共聚合反应。结果表明，温度、助乳化剂分子量、助乳化剂浓度、乳化剂浓度、引发剂浓度、不同助乳化剂对聚合反应速率和聚合物颗粒大小均有影响，对常规乳液聚合与细乳液聚合的差异进行了比较，并测定了聚合物胶乳的耐盐稳定性。     

无三苯CR/SBS/MMA/BA自交联鞋用胶粘剂的研制

采用复合引发剂 ,以N 羟甲基丙烯酰胺 (NAM )及丙烯酸 (AA)为功能单体 ,与CR、苯乙烯 丁二烯嵌段共聚物 (SBS)、甲基丙烯酸甲酯 (MMA)和丙烯酸丁酯 (BA)进行多元共混接枝共聚 ,再配以混合型增粘树脂 ,研制出不含苯、甲苯和二甲苯 (简称三苯 )自交联环保型鞋用胶粘剂。探讨了SBS用量、MMA/BA配比、功能单体NAM及AA用量对胶粘剂粘合性能的影响。结果表明 ,CR/SBS/MMA/BA/AA/NAM自交联型接枝胶粘剂对非极性鞋材的粘合性能明显优于CR/MMA/BA三元接枝胶和CR/SBS/MMA/BA四元接枝胶。     

Synthesis of CaCO3–P(MMA–BA) nanocomposite and its application in water based alkyd emulsion coating

As part of broader effort to synthesize a new class of water-based composite, hybrid emulsion polymerization was carried out with acrylic monomers [methyl methacrylate (MMA), n-butyl acrylate (BA)]. Nanocomposite of P(MMA–BA)/nano CaCO₃ was synthesized by in situ emulsion polymerization. Water-based alkyd coating with various proportions nano CaCO₃, P(MMA–BA) and its nanocomposite was formulated. Extent of polymerization with and without nano CaCO₃ was measured using gravimetric method. Thermal properties of neat polymer, nanocomposite and coating films were evaluated by TGA and DSC, DTA analysis. Uniform dispersion of nano CaCO₃ in polymer matrix was ensured from SEM/TEM images. Incorporation of nanoparticles to hybrid polymer and nanocomposite to alkyd emulsion showed significant enhancement in mechanical and thermal properties. Dual role of nanocomposite in coating; as a partial binder and a filler to improve property profile of neat coating has been reported.     

甲基丙烯酸甲酯/丙烯酸丁酯的无皂乳液共聚

以甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)为主要原料,过硫酸铵为引发剂,进行无皂乳液聚合.结果表明:在不添加乳化剂的情况下,当MMA/BA=1:1、引发剂用量为0.24%、反应温度为80℃、反应时间8.0h时,所得乳液最稳定,单体转化率为81.84%,此无皂乳液对牛皮纸的粘接性比常规乳液好.     

Synthesis of Bis(1H, 1H, 2H, 2H‐perfluoro‐octyl)methylenesuccinate copolymers and their application on cotton fabrics

Bis(1H, 1H, 2H, 2H‐perfluoro‐octyl)methylenesuccinate (FOM)/ethyl acrylate (EA)/methyl methacrylate (MMA) copolymer (FOME) latexes, FOM/butyl acrylate (BA)/MMA copolymer (FOMB) latexes, and FOM/octyl acrylate (OA)/MMA copolymer (FOMO) latexes were synthesized by continuous emulsion polymerization. Solution polymerization was also carried out to prepare FOMB. The influences of fluorine content and curing conditions on the surface properties of polymer films were discussed. The water and oil repellency of cotton fabrics treated with the FOM copolymers was better than that of conventional poly(fluoroalkyl acrylate)s containing the same fluorinated chain. The polymer films or the treated fabrics were characterized by Fourier transform infrared, scanning electron microscope, atomic force microscopy, thermogravimetric analysis, x‐ray photoelectron spectrometry, and wide angle x‐ray diffraction. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci, 2013     

VAc/VoeVa/DAAM三元共聚乳液的制备与性能研究

以VAE[醋酸乙烯酯(VAc)-乙烯共聚物]为种子乳液、聚乙烯醇(PVA)为保护胶体、叔碳酸乙烯酯(VoeVa10)为VAc的共聚单体、OP-10为乳化剂、己二酰肼(ADH)/双丙酮丙烯酰胺(DAAM)为交联体系和叔丁基过氧化氢/甲醛次硫酸钠为氧化还原型引发剂,采用种子乳液聚合法制备了VAc/VoeVa10/DAAM共聚乳液;然后在反应后期加入后交联剂(ADH),得到改性聚醋酸乙烯酯(PVAc)乳液。结果表明:当w(PVA1788+PVA1799)=3%、m(PVA1788)∶m(PVA1799)=1∶1、m(VoeVa10)∶m(VAc)=(10～15)∶100、w(氧化剂)=0.3%、w(VAE)=10%、w(OP-10)=2%、m(ADH)∶m(DAAM)=(0.5～1.5)∶1.0且w(DAAM)=2%时,相应乳液具有优异的耐水性和稳定性,并且其涂膜柔韧性和粘接性能俱佳。     

SBS／MMA／BA／MAA四元接枝共聚及其产物粘接性能

研究了SBS与甲基丙烯酸（MAA）和甲基丙烯酸甲酯（MMA）,丙烯酸丁酯（BA）的四元接枝共聚,探讨了MMA／BA质量比,MMA与BPO用量,反应时间,反应温度及固化时间对粘接性能的影响,并将该四元接枝胶的性能与三元胶和SBS／MMA／BA／AA四元胶进行了比较,结果发现：该四元胶对聚烯烃的粘接强度及室温固化性能优于SBS／MMA／BA三元胶,尤其与异氰酸酯配合使用时,其效果更佳,而且该四元胶的粘接强度,耐水及耐热性能均优于SBS／MMA／BA／AA四元胶。     

MMA/BA共聚物改性的水性聚氨酯的合成与表征

以1, 4-丁二醇 (BDO)、二羟甲基丙酸 (DMPA) 和己二酸二酰肼 (ADH) 为扩链剂，以甲基丙烯酸甲酯 (MMA) 和丙烯酸丁酯 (BA) 改性聚氨酯 (PU)，得聚氨酯-丙烯酸酯复合乳液 (PUA).研究了BA和二丙酮丙烯酰胺 (DAAM) 对乳液及膜性能和粘接性能的影响，并用傅立叶红外光谱 (FTIR)仪对PUA复合乳液进行了结构表征.实验结果表明当BA含量为4.0%～6.0%，DAAM含量为2.0%～3.0%时，乳液和膜性能较好，黏度性能较佳.用该乳液配制的胶黏剂对木材有很好的粘接性能.     

The role of methyl methacrylate on branching and gel formation in the emulsion copolymerization of BA/MMA

The effect of the monomer ratio on the microstructure of BA/MMA emulsion copolymers was investigated. Monomer ratios spanned from pure BA used for adhesives to 50/50 wt/wt BA/MMA copolymers used for coatings. The gel content varied from 55% for pure BA to nil for the 50/50 copolymer. The branching level was reduced from 2.6% for pure BA to 0.3% for a 75/25 BA/MMA copolymer. The mechanisms responsible for the reduction of gel content can be found in the lower reactivity of the MMA terminated chains for hydrogen abstraction, the absence of abstractable hydrogens in the MMA units and the fact that MMA radicals terminate predominantly by disproportionation. The reduction of the level of branches is mainly due to the lower reactivity of MMA for intramolecular transfer and the lower instantaneous conversions that favored propagation over backbiting.     

无三苯CR/SBS/MMA/BA自交联环保型鞋用胶的合成与表征

在不含"三苯"的溶剂中,研究了氯丁橡胶(CR)、SBS、甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、自交联剂N-羟甲基丙烯酰胺(NAM)及丙烯酸(AA)的多元共混接枝共聚,着重讨论了SBS用量、MMA/BA配比,复合交联剂NAM及AA用量、复合引发剂用量、聚合温度和聚合时间对胶粘剂粘合性能的影响,并用红外光谱对接枝产物进行了表征。研究结果表明:所研制的CR/SBS/MMA/BA/AA/NAM自交联环保型接枝胶对非极性鞋材的粘接性能优良。     

食品包装材料用无毒干法覆膜胶乳液的研制

以醋酸乙烯酯(VAc)和甲基丙烯酸甲酯(MMA)为硬单体、丙烯酸丁酯(BA)为软单体、交联单体(TM-200)/丙烯酸(AA)为复合交联剂、叔丁基过氧化氢(TBHP)/甲醛合次硫酸钠(吊白块)为氧化-还原型引发剂、可聚合型阴离子乳化剂(SVS-25)为环保型乳化剂和Gohsefimer Z-210为改性保护胶体,采用乳液聚合法制备出食品包装材料用无毒干法覆膜胶。研究结果表明:采用减压脱除及后添加氧化-还原型引发剂,可使覆膜胶中残余单体含量降至0.01%以下;当m(VAc)∶m(MMA)∶m(BA)=30∶10∶60、乳化剂中m(SVS-25)∶m(Gohsefimer Z-210)=1∶1、w(乳化剂)=2.0%和w(氧化-还原型引发剂)=0.20%时,覆膜胶的综合性能相对最好。     

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     

水性油墨用室温自交联纯丙乳液的合成及应用

以甲基丙烯酸甲酯(MMA)、丙烯酸异辛酯(2-EHA)、甲基丙烯酸(MAA)、双丙酮丙烯酰胺(DAAM)为聚合单体,己二酰肼(ADH)为交联剂,采用半连续种子乳液聚合法合成软核硬壳结构的水性纯丙乳液。利用ATR-FTIR、TEM、GPC、TG、DMA表征水性纯丙乳液的结构和性能。结果表明:乳液成膜过程中DAAM中的—CO—与ADH中的—NHNH_2发生反应,交联度增加,提高了乳液膜的耐水性、热稳定性、玻璃化转变温度和油墨在双向拉伸聚丙烯(BOPP)薄膜上的附着力。当DAAM用量(以MMA和2-EHA的总质量为基准,下同)从0增加到2%,m(ADH)∶m(DAAM)=0.7∶1.0时,乳液膜的吸水率从24.2%降到7.6%,油墨的附着力从87%升至100%;当m(ADH)∶m(DAAM)从0∶1增加到0.7∶1.0,DAAM用量为2%时,乳液膜的吸水率从28.1%降至7.6%,油墨的附着力从0增至100%。当DAAM用量为2%,m(ADH)∶m(DAAM)为0.7∶1.0时,水性纯丙乳液可用作环保型水性油墨的连接料。     

Synthesis and characterization of low-temperature self-crosslinkable acrylic emulsion for PE film ink

A low-temperature self-crosslinkable acrylic emulsion was synthesized by semi-continuous emulsion polymerization technology using methyl methacrylate (MMA), butyl acrylate (BA), acrylic acid (AA) and diacetone acrylamide (DAAM) as monomers and adipic dihydrazide (ADH) as crosslinker. Transmission electron microscope (TEM) micrograph disclosed spherical emulsion particles possess core–shell structure. Fourier transform infrared (FTIR) spectrogram showed that crosslinking reaction between CO groups of DAAM and NHNH₂ groups of ADH can occur during coating film formation at low temperature, even at room temperature. Differential scanning calorimeter (DSC) analysis indicated that glass transition temperature (Tg) of the crosslinked film is increased by 5 °C. Thermogravimetric analysis (TGA) curves demonstrated that self-crosslinking reaction improves thermal stability of film. As DAAM content increased from 0% to 2%, water absorption ratio of film decreased from 26.2% to 7.4%, adhesion ratio on the PE thin film increased from 0% to 97%. While the n(ADH)/n(DAAM) ratio increased from 0:1 to 0.8:1, crosslinking density of films was increased from 0% to 88%, water absorption ratio decreased from 36.5% to 7.4% and adhesion ratio on the PE thin film increased from 0% to 97%. The optimal DAAM content and n(ADH)/n(DAAM) ratio was 2% and 0.8:1 in this experiment. The emulsion has good potential application in water-based ink for PE film.     

Synthesis and characterization of poly(methyl methacrylate–butyl acrylate–acrylic acid)/polyaniline core–shell nanoparticles in miniemulsion media

Conductive polymer particles, polyaniline (PANI)‐coated poly(methyl methacrylate–butyl acrylate–acrylic acid) [P(MMA–BA–AA)] nanoparticles, were prepared. The P(MMA–BA–AA)/PANI core–shell complex particles were synthesized with a two‐step miniemulsion polymerization method with P(MMA–BA–AA) as the core and PANI as the shell. The first step was to prepare the P(MMA–BA–AA) latex particles as the core via miniemulsion polymerization and then to prepare the P(MMA–BA–AA)/PANI core–shell particles. The aniline monomer was added to the mixture of water and core nanoparticles. The aniline monomer could be attracted near the outer surface of the core particles. The polymerization of aniline was started under the action of ammonium persulfate (APS). The final product was the desired core–shell nanoparticles. The morphology of the P(MMA–BA–AA) and P(MMA–BA–AA)/PANI particles was characterized with transmission electron microscopy. The core–shell structure of the P(MMA–BA–AA)/PANI composites was further determined by Fourier transform spectroscopy and ultraviolet–visible measurements. The conductive flakes made from the core–shell latexes were prepared, and the electrical conductivities of the flakes were studied. The highest conductivity of the P(MMA–BA–AA)/PANI pellets was 2.05 S/cm. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Study on swelling behavior and pervaporation properties of AA–MMA–BA copolymers for separation of methanol/MTBE/C5 mixtures

In this study, the copolymers with different ratios of AA(acrylic acid)–MMA(methyl methacrylate)–BA (butyl acrylate) are synthesized to prepare pervaporation membrane for the separation of methanol/MTBE (methyl tert‐butyl ether)/C₅ mixtures. Swelling experiment of these copolymers in pure methanol, MTBE, C₅, and methanol/MTBE mixtures are carried out, respectively. The results show that there is a strong interaction between MTBE and copolymer with high content of BA. The pervaporation characteristics of the membranes prepared with different copolymer are measured in the separation of methanol/MTBE mixture. The experimental results show that the pervaporation ability changes with swelling degree in the same direction. The copolymers are characterized by FTIR. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2267–2271, 2003     

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。