氧化还原引发体系下双层自交联丙烯酸核壳乳液的合成
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1.郑州大学 化工学院,河南 郑州 450001;2.郑州大学 化工学院,河南 郑州 450001

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Synthesis of Bilayer Self-Crosslinking Acrylic Core-Shell Emulsions in Redox Initiation System
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    摘要:

    以苯乙烯(St)、甲基丙烯酸甲酯(MMA)为硬单体,丙烯酸丁酯(BA)为软单体,乙烯基三甲氧基硅烷(A-171)和双丙酮丙烯酰胺(DAAM)分别为核层和壳层各自的交联单体,合成室温下自交联改性核壳结构丙烯酸酯乳液,探究引发体系的选择与用量、交联单体种类和添加量对乳液聚合的影响。通过衰减全反射傅里叶变换红外光谱证明交联单体成功交联,通过Zeta电位分析、透射电镜对乳液进行表征,证明成功合成了均一的核壳乳液。结果证明,以半连续种子乳液聚合法聚合,引发剂KPS和NaHSO3质量比为2:1、引发剂用量为0.4%、核层自交联单体乙烯基三甲氧基硅烷(A-171)和壳层自交联单体双丙酮丙烯酰胺(DAAM+ADH)的质量分数分别为3%和2%,乳液的稳定性、耐水性和成膜性良好,转化率在90%以上,吸水率为6.87%,钙离子稳定性合格。与非核壳无交联单体乳液进行对比,热重分析表明热分解温度提高了41 ℃,缓解了传统水性丙烯酸酯乳液涂层耐水性差、耐溶剂性差、“热粘冷脆”的问题。

    Abstract:

    Using styrene (St) and methyl methacrylate (MMA) as hard monomer, butyl acrylate (BA) as soft monomer, vinyltrimethoxysilane (A-171) and diacetone acrylamide (DAAM) as crosslinking monomer in the core and shell layers, respectively, the self-crosslinking modified core-shell acrylate emulsions were synthesized at room temperature. The effects of initiator type and dosage, crosslinking monomer addition on emulsion polymerization were investigated. Successful cross-linking of the cross-linking monomers was proved by ATR-FTIR, and the emulsions were characterized by DLS and TEM, which proved the successful synthesis of homogeneous core-shell emulsion. The results prove that the emulsions were polymerized by semi-continuous seed emulsion polymerization with the initiator m(KPS):m(NaHSO3)=2:1, the initiator dosage of 0.4%, and the mass fractions of self-cross-linking monomer vinyltrimethoxysilane (A-171) in the core layer and self-cross-linking monomer bis (acetone acrylamide) (DAAM+ADH) in the shell layer of 3% and 2%, respectively, and the emulsions have good stability, water resistance and film-forming property, with the conversion rate above 90%, water absorption rate above 90%, the water absorption rate is 6.87%, and the calcium ion stability is qualified. Compared with the non-crosslinked monomer emulsion without core-shell, the thermal decomposition temperature of TG is increased by 41 ℃, which alleviates the problems of poor water resistance, poor solvent resistance, and "hot sticking and cold brittleness" of water-based ink coating.

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  • 收稿日期:2023-12-27
  • 录用日期:2024-12-13
  • 网络出版日期:2024-12-28
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