PREPARATION AND CHARACTERIZATION OF AFFINITY POLYMER BASIC MICROSPHERES BY SOAP-FREE EMULSION POLYMERIZATION

Poly(styrene-co-glycidyl methacrylate) latex microspheres with uniform size and high-density epoxy groups on the surface were prepared by soap-free emulsion polymerization with batch wise operation mode in the presence of 2.2′- azobis(2-methylpropionamidine) dihydrochloride as an initiator.The kinetics of soap-free emulsion polymerization and the effects of polymerization factors were examined.In addition,the optimum polymerization conditions of poly(styrene-co- glycidyl methacrylate) latex microspheres for...

SYNTHESIS OF SOAP-FREE ACRYLIC HYDROSOLS

Poly(methyl methacrylate/ethyl acrylate/acrylic acid) hydrosols were prepared by employing soap-free polymerization, and (acrylic acid/butyl acrylate) oligomer was used as the polymeric surfactant. The effect of reaction condition on the morphology and particle size of the hydrosols was investigated. The minimum amount of acrylic acid in the hydrosols is 2%. The maximum weight average molecular weight (M-w) of polymer that assures soap-free emulsion conversion into hydrosol is about 1.2 x 10(5)-1.3 x 10(5). The particle transforming process was investigated, and an obvious change of particle diameter and morphology was observed.

Influences of Electrolytes on the Soap-free Emulsion Copolymerization of St-MMA-AA

Monodisperse functional polymer microspheres with different particle size and with clean surface were prepared by batch soap-free emulsion polymerization of styrene, methyl methacrylate and acrylic acid in the presence of salts, and the influences of type and amount of electrolytes on polymerization process and particle morphology were investigated. Results showed that there was a critical concentration for different electrolyte to make polymerization process and the resultant emulsion stable, and the particle size increased with the increase of electrolyte concentration. The effect of metal ions was Ca^2＋〉〉K^＋〉Na^＋〉Li^＋, and the effect of haloids was Br〉Cl〉F. Keywords： Electrolyte, soap-free emulsion polymerization, polystyrene, latex particle morphology.

Preparation of Self-crosslinked Fluorocarbon Polymer Emulsion with Core-shell Structure by the Method of Soap-free Emulsion Polymerization

Using methyl methacrylate （MMA）, butyl acrylate（BA） and hexafluorobutyl acrylate（HFBA） as main raw materials, we prepared self-crosslinked fluorocarbon polymer emulsion with core-shell structure via soap-free emulsion polymerization when the conception of particle design and polymer morphology was adopted. Moreover, the influence of mole ratio of BA to MAA, pH value on the oligomer was studied. And the effects of the added amount of oligomer, self-crosslinked monomer and HFBA, mass ratio of BA to MMA, reaction temperature and the initiator on the polymerization technology and the performance of the product, were investigated and optimized. The structure and performance of the fluorocarbon polymer emulsion were characterized and tested with FTIR, TEM, MFT and contact angle and water absorption of the latex film. The experimental results show that the optimal conditions for preparing fluorocarbon polymer emulsion are as follows： for preparing the oligomer, tool ratio of BA to MAA is equal to 1.0 ： 1.60, and pH value is controlled within the range of 8.0 and 9.0; for preparing fluorocarbon polymer emulsion, the added amount of oligmer[P（BA/MANa）] is 6%; mass ratio of BA to MMA is 40 ＂ 60; the added amount of self-crosslinked monomer is 2%, the added amount of HFBA is 15 %; reaction temperature is 80 ℃; the mixture of potassium persulfate and sodium bisulfite is used as the initiator. The film-forming stability of the fluorocarbon polymer emul- sion and the performance of the latex film, which is prepared with the soap-free emulsion polymerization, are better than that prepared with the conventional emulsion polymerization.

Synthesis and Characterization of Poly (Methyl Methacrylate)/Polyethylenimine Grafting Core-Shell Nanoparticles for CO2 Adsorption Using Soap-Free Emulsion Copolymerization

Unlike previous emulsion polymerization, we used grafting reactions in soap-free emulsion systems. In this study, we synthesized grafted PMMA/PEI core-shell nanoparticles by varying the MMA/PEI content and molecular weight of PEI (Mn = 600, 8000, and 10,000). The size and morphology of the core-shell nanoparticles were characterized by a particle size analyzer and scanning electron microscopy. The nanoparticles were 178 - 408 nm in diameter and swelled in water or methanol by 30 - 75 nm. The size of the nanoparticles increased with MMA contents, whereas the size distribution progressively became homogeneous with increasing molecular weight of PEI. Lastly, we measured CO2 adsorption capacity of the grafted PMMA/PEI core-shell nanoparticles, and we found the capacity to be limited at a level of 0.69 mg, which occurred for nanoparticles prepared from emulsions at a pH value of 11.

INFLUENCES OF ACID POST-TREATMENT ON THE MORPHOLOGY OF SOAP-FREE P(MMA-EA-MAA)PARTICLES PREPARED BY SEEDED EMULSION POLYMERIZATION

Soap-free poly（methyl methacrylate-ethyl acrylate-methacrylic acid） latex particles with narrow size distribution were synthesized by seeded emulsion polymerization, and the porous particles were created by a stepwise alkali/acid treatment method. Effects of acid treatment conditions on the particle morphology were investigated. Results show that one to three pores were formed inside most of particles after post-treatment. At pH 7.0, when the treatment temperature was lower than 70℃, the size of particles and the volume of pores remained almost unchanged, and these two values increased significantly when the temperature was higher than 70℃. Both the particle size and the pore volume decreased with the increase of initial pH value and treatment time in the acid treatment. As the pH was below 4.0 and the treatment time was longer than 180 min, the particles shrunk in size.

DESIGN AND CONTROL OF SOAP-FREE HYDROPHILIC-HYDROPHOBIC CORE-SHELL LATEX PARTICLES WITH HIGH CARBOXYL CONTENT IN THE CORE OF THE PARTICLES

Soap-flee hydrophilic-hydrophobic core-shell latex particles with high carboxyl content in the core of the particles were synthesized via the seeded emulsion polymerization using methyl methacrylate （MMA）, butyl acrylate （BA）, methacrylic acid （MAA）, styrene （St） and ethylene glycol dimethacrylate （EGDMA） as monomers, and the influences of MMA content used in the core preparation on polymerization, particle size and morphology were investigated by transmission electron microscopy, dynamic light scattering and conductometric titration. The results showed that the seeded emulsion polymerization could be carried out smoothly using ＂starved monomer feeding process＂ when MAA content in the core preparation was equal to or less than 24 wt%, and the encapsulating efficiency of the hydrophilic P（MMA-BA-MAA- EGDMA） core with the hydrophobic PSt shell decreased with the increase in MAA content. When an interlayer of P（MMA- MAA-St） with moderate polarity was inserted between the P（MMA-BA-MAA-EGDMA） core and the PSt shell, well designed soap-free hydrophilic-hydrophobic core-shell latex particles with 24 wt% MAA content in the core preparation were obtained.

PREPARATION OF MICRON-SIZED NONSPHERICAL POLYSTYRENE/POLY(STYRENE-co-ETHYLENEGLYCOL DIMETHACRYLATE) PARTICLES BY SEEDED SOAP-FREE EMULSION POLYMERIZATION

Micron-sized nonspherical polymer particles having different morphologies were synthesized by seeded soap-free emulsion polymerization of styrene （St） and ethyleneglycol dimethacrylate （EGDMA, used as a crosslinker） on spherical, linear polystyrene （PS） seed particles. The morphology of the resulting PS/poly（St-co-EGDMA） particles was dependent on the crosslinker concentration and polymerization temperature.

Synthesis of submicron-sized peanut-shaped poly(methyl methacrylate)/polystyrene particles by seeded soap-free emulsion polymerization

亚微米大小塑造花生(甲基 methacrylate ) poly， /polystyrene (PMMA/PS ) 粒子被苯乙烯的播种没有肥皂的乳剂聚合成功地在球形的 crosslinked PMMA 种子粒子上综合。获得的塑造花生的粒子显示出新奇内部形态学：PS 阶段形成了连接了到把 PMMA 核心被 PS 壳装入箱内的另外的领域的一个领域。

IBVE/AANa/VAc无皂乳液的合成与性能

本文以异丁基乙烯基醚、丙烯酸钠和醋酸乙烯酯为反应单体合成无皂乳液。研究了AANa的用量对乳液稳定性的影响,考察了VAc/IBVE的比例与聚合物性能的关系,同时分析了乳胶粒的形貌。结果表明,亲水性单体AANa对乳液的稳定性、粒径大小影响较大。调整反应单体VAc/IBVE的比例可以得到不同分子量、不同玻璃化转变温度的聚合物,该无皂乳液具有明显的核壳结构。

聚丙烯酸酯无皂乳液的构建及对水性油墨性能的影响

以丙烯酸(AA)、丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)、丙烯酸羟丙酯(HPA)、2-甲基丙烯酸羟乙酯(HEMA)、乙烯基三异丙氧基硅烷(A-173)为单体,过氧化苯甲酰(BPO)、过氧化苯甲酸叔丁酯(TBPB)为引发剂,合成了丙烯酸酯大分子乳化剂,再通过无皂乳液聚合法合成了聚丙烯酸酯无皂乳液,将其与颜料等混合制备了水性油墨。采用FTIR、DSC、TEM、SEM对聚合物的结构及性能进行了表征,考察了不同BPO用量对丙烯酸酯大分子乳化剂的影响,不同AA添加量对乳液及水性油墨的影响。结果表明:当BPO用量为单体总质量的4.18%时,丙烯酸酯大分子乳化剂具有最低表面张力40.43mN/m;当AA添加量为单体总质量的1.00%时,聚丙烯酸酯无皂乳液具有合格的储存稳定性,乳胶膜拉伸强度可达5.00 MPa,断裂伸长率为200%,玻璃化转变温度为18.5℃,所制备的水性油墨黏度为23.79mPa·s,附着牢度90.75%,耐摩擦性4.5级。

生态酶处理及新型活性染料染色短流程与免皂洗后处理工艺生产实践

前处理、染色到后处理都需经过染料、助剂等大量化学处理过程,各工序能源、热能和水的消耗量都很大,废水的电导率、COD高,污水处理难度大。通过大量生产实践,总结分析了公司自主开发的生态酶前处理工艺、新型活性染料染色短流程工艺及免皂洗后处理工艺,该前处理、染色、后处理工艺具备低温柔和、短流程、免皂洗等优点,大幅度降低了电导率、COD、污染和排放。

聚对苯乙烯磺酸微球的绿色制备及催化合成生物柴油

以水为介质、苯乙烯(St)为基体单体、二乙烯苯(DVB)为交联单体、对苯乙烯磺酸钠(Na SS)为功能单体、甲基丙烯酸(MAA)为水溶性单体、过硫酸钾(KPS)为引发剂,采用无皂乳液聚合法制备了聚对苯乙烯磺酸微球(PSS)。利用FTIR、XPS、SEM、TGA和DSC对其进行了表征,并对其粒径、Zeta电位、比表面积、酸密度进行了考察,探讨了Na SS、DVB和KPS用量对PSS结构、性能的影响。当H_(2)O为90m L、St为76.9 mmol、MAA为9.3 mmol、NaSS为0.7mmol、DVB为7.7 mmol、KPS为0.7mmol时,制备的PSS-3粒径均匀且酸密度较高。然后,将PSS-3作为固体酸催化剂,用于催化油酸/甲醇酯化合成生物柴油(油酸甲酯)。结果表明,当甲醇/油酸的物质的量比为10∶1、PSS-3用量为油酸质量的2%、反应温度为80℃、反应时间为6h时,油酸的转化率可达86.4%。PSS-3作为固体酸催化剂具有较好的重复使用性能,循环使用4次后油酸转化率没有明显下降。

基于呋喃、马来酰亚胺Diels-Alder反应的自修复水性聚丙烯酸酯涂料的制备及性能研究

基于呋喃和马来酰亚胺之间的可逆Diels-Alder(DA)反应,成功制得一种通过热驱动而具备自修复特性的水性聚丙烯酸酯涂料,并对自修复的条件进行了探索和优化。首先合成带呋喃官能团的丙烯酸酯单体(FEEMA),将其与常用的丙烯酸单体无皂乳液共聚合,得到稳定的水性丙烯酸酯乳液,并对其进行红外光谱、凝胶渗透色谱和粒径测试。其次设计合成出能够水分散的、带聚醚链的双马来酰亚胺(D-400-BMI),使其与水性丙烯酸酯乳液进行Diels-Alder反应得到水性聚丙烯酸酯交联膜。利用红外光谱及差示扫描量热法跟踪不同条件下的Diels-Alder反应和retro-DA过程,结果表明当聚合物中的FEEMA质量分数为30%、甲基丙烯酸甲酯与丙烯酸丁酯质量比为1∶5时,由自制的较软链段分子D-400-BMI制备的交联膜有较好的修复性能。交联膜被划伤后,经140℃热处理再缓慢冷却至室温,可对表面划伤和摩擦痕迹有良好的修复效果。此外,制备的交联膜还具备良好的耐热性能和机械性能,在表面涂层划痕和微裂纹自修复方面有潜在应用前景。

氟硅改性聚丙烯酸酯乳液整理亚麻织物的研究

研究氟硅改性聚丙烯酸酯无皂乳液的性能,并将其用于亚麻织物整理。以壬基酚聚氧乙烯醚硫酸铵为乳化剂,采用无皂乳液聚合法使丙烯酸酯单体与甲基丙烯酸十二氟庚酯、乙烯基三甲氧基硅烷接枝共聚,制备了氟硅改性聚丙烯酸酯无皂乳液。利用扫描电子显微镜、原子力显微镜、X射线电子能谱仪等对乳液的性能和结构进行了表征,并对整理后的亚麻织物进行傅里叶红外光谱和热重分析的表征以及性能测试。结果表明:制备的乳液平均粒径93 nm,Zeta电位值-45.7 mV;乳胶膜具有良好的疏水表面结构,氟、硅元素大量富集在胶膜表面,降低了其表面能。整理后的亚麻织物具有优良的热稳定性,柔软性有一定程度改善。认为:制备的乳液可用于亚麻织物的柔软改性整理。

自修复纤维素纳米晶改性含氟聚丙烯酸酯无皂乳液的制备和性能

采用无皂乳液技术合成了自修复纤维素纳米晶改性含氟聚丙烯酸酯无皂乳液,并将乳液用于织物整理。研究了不同丙烯酸十八酯(SA)用量下的乳胶粒粒径、乳胶膜的疏水疏油性、力学性能和自修复性能,以及整理织物的疏水疏油性和自修复性能。结果表明:当SA质量分数为1.0%时,乳胶粒粒径较小,水/油接触角分别为104.35°和70.25°,拉伸强度为4.17 MPa,断裂伸长率为720.88%,自修复效率为91.49%,表现出良好的疏水疏油性、力学性能和自修复性能。经乳液整理的织物水/油接触角分别为150.70°和127.40°,呈现出优异的疏水疏油性,以及较好的划痕和表面疏水性的自修复性能。

半乳糖基温敏微凝胶药物缓释研究

通过无皂乳液聚合法制备半乳糖基温敏微凝胶,借助傅里叶变换红外光谱仪、核磁共振氢谱仪、场发射扫描电子显微镜和动态光散射等对微凝胶的结构进行表征。以阿霉素为药物模型,考察了温敏微凝胶的体外释放行为。结果表明:当单体2-甲基-2-丙烯酸-2-(2-甲氧基乙氧基)乙酯(DEGMA)与6-O-乙烯基己二酸-D-吡喃类半乳糖酯(OVNGal)摩尔比为40∶1,交联剂质量分数为1%时,微凝胶粒径均匀分布在400~700nm范围;37℃时7d累计释放率达到约50%。