壳聚糖季铵盐基丙烯酸酯无氟防油剂的合成与高抗油高疏水纸的构建
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南京林业大学

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TS727+.3;TQ352

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国家自然科学基金资助项目


Synthesis of chitosan quaternary ammonium acrylate fluorine-free oil-proof agent and construction of high oil proof and high hydrophobic paper
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Nanjing Forestry University

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Supported by the National Natural Science Foundation of China

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    摘要:

    以生物质壳聚糖季铵盐(HACC)为功能单体,丙烯酸(AA)、丙烯酸丁酯(BA)、丙烯酸异辛酯(EHA)为软单体,甲基丙烯酸甲酯(MMA)为硬单体,过硫酸铵(APS)为引发剂,采用半连续种子预乳液法,制备了壳聚糖季铵盐基丙烯酸酯无氟防油剂(HACC-A),采用表面涂布法,将HACC-A与烷基烯酮二聚体(AKD)复配涂布构建防水防油AKD-HACC-A涂布纸。考察了乳化剂类型、反应时间、引发剂用量、反应温度和HACC用量等对HACC-A粒径分布和贮存稳定性的影响。基于FTIR、SEM、EDS等表征和纸张防水防油、物理性能、机械强度、印刷效果测试,考察了HACC-A涂布量、HACC-A与AKD复配比例对涂布纸的60 s Cobb值、Kit防油等级等参数的影响。结果表明,HACC-A最优合成工艺条件为:质量分数5%(占单体总质量的百分数,下同)的OP-10为乳化剂,反应温度70 ℃,引发剂APS用量0.8%(占单体总质量的百分数,下同),反应时间2 h,在该条件下制备的HACC-A乳液粒径约为200 nm,且分布较窄,蓝光明显,可长时间(60 d)稳定储存;当HACC用量为5 g,HACC-A涂布量为6 g/m2时,经HACC-A涂布后的纸张60 s Cobb值为54 g/m2,Kit防油等级为6级,满足食品包装标准;当m(HACC-A)∶m(AKD)=1∶1,涂布量为6 g/m2时,AKD-HACC-A涂布纸60 s Cobb值为30 g/m2,Kit防油等级为10级,对常见油脂(常温和105 ℃的食用油以及辣椒油)、有机溶剂(乙醇和丙酮)和碱性溶液(盐酸和NaOH溶液)表现出良好的阻隔性能,防油性能优于聚乙烯(PE)淋膜纸(Kit防油等级6级),接近含氟防油纸(Kit防油等级11级)的防油性能。HACC表面的活性基团氨基和羟基以及良好的成膜性为提升防油剂AKD-HACC-A的性能起到了关键作用。

    Abstract:

    Using biochitosan quaternary ammonium salt (HACC) as functional monomer, acrylic acid (AA), butyl acrylate (BA), isooctyl acrylate (EHA) as soft monomer, methyl methacrylate (MMA) as hard monomer, and ammonium persulfate (APS) as initiator, semi-continuous seed pre-emulsion method was adopted. The water-proof and oil-proof AKD-HACC-A coating paper was prepared by using the method of surface coating with HACC-A and alkyl ketene dimer (AKD). The effects of emulsifier type, reaction time, initiator dosage, reaction temperature and HACC dosage on the particle size distribution and storage stability of HACC-A were investigated. Based on the characterization of FTIR, SEM and EDS, as well as the tests of water and oil resistance, physical properties, mechanical strength and printing effect of the paper, the influences of the coating amount of HACC-A, the ratio of HACC-A and AKD on the Cobb value of the coated paper and the oil resistance grade of kit were investigated. The results showed that the optimal synthesis process of HACC-A was as follows: OP-10 with a mass fraction of 5% (percentage of the total weight of monomer, the same below) is the emulsifier, the reaction temperature is 70 ℃, the amount of initiator APS is 0.8% (percentage of the total weight of monomer, the same below), and the reaction time is 2 h. Under such conditions, the particle size of HACC-A emulsion prepared is about 200 nm, the distribution is narrow, and the blue light is obvious. Stable storage for a long time (60 d); When the amount of HACC is 5 g and the amount of coating is 6 g/m2, the 60 s Cobb value of the paper after HACC-A coating is 54 g/m2, and the kit oil-proof grade is 6, which meets the food packaging standard. When m(HACC-A)∶m(AKD) = 1∶1, the coating amount is 6 g/m2. After coating the paper, the Cobb value of AKD-HACC-A coated paper 60 s is 30 g/m2, and the kit oil proof grade is 10. It showed good barrier properties to common oils (edible oil and pepper oil at room temperature and 105 ℃), organic solvents (ethanol and acetone) and alkaline solutions (hydrochloric acid and NaOH solution), and its oil proof performance was better than that of PE coated paper (Kit oil proof grade 6) and close to that of fluorinated paper (Kit oil proof grade 11). The active groups of amino and hydroxyl groups on the surface of HACC and good film formation play a key role in improving the performance of oil repellant AKD-HACC-A.

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王雯璐,景宜,包康.壳聚糖季铵盐基丙烯酸酯无氟防油剂的合成与高抗油高疏水纸的构建[J].精细化工,2025,42(5):

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  • 收稿日期:2024-05-07
  • 最后修改日期:2024-07-09
  • 录用日期:2024-06-06
  • 在线发布日期: 2025-04-27
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