• ISSN 1008-505X
  • CN 11-3996/S

棕榈油基可降解包膜材料的制备及性能研究

Preparation of palm oil-based degradable coating materials and the property study

  • 摘要:
    目的 植物油多元醇的物化性质是影响聚氨酯材料微观结构和宏观性能的主要因素。尝试通过改变亲核试剂甲醇用量调节棕榈油多元醇羟值、黏度等物化指标,研究多元醇物性、聚氨酯性能与肥料养分控释性能之间的关联性,为优化棕榈油基聚氨酯包膜性能,降低可降解包膜肥料成本提供理论依据。
    方法 以饱和度高的棕榈油为起始原料,采用环氧开环法,通过调节甲醇用量(醇油比为0.4∶1~1∶1),合成了4种棕榈油多元醇,标记为POP1、POP2、POP3、POP4;以上述多元醇为原料,通过原位反应成膜技术制备了4种棕榈油基可降解包膜尿素,依次标记为PCU1、PCU2、PCU3、PCU4。研究了甲醇用量对棕榈油多元醇羟值、酸值、黏度、分子量及官能度的影响,借助傅里叶红外光谱(FTIR)、核磁共振氢谱(1H NMR)、扫描电子显微镜(SEM)和热重(TG)等表征手段,系统分析了甲醇用量对棕榈油多元醇及其膜材微观结构的影响。进一步采用质量法和水泡法,测试包膜的吸水率和肥料氮素累积释放率,分析甲醇用量对包膜耐水性和控释性的影响。最后,通过包括含3个包膜浓度的发芽试验,评价包膜的安全性。
    结果 通过调节甲醇用量合成了羟值范围在101~132 mgKOH/g、黏度范围在365~618 mPa·s、官能度在1.89~2.73的棕榈油多元醇。FTIR 和1H NMR分析结果表明,棕榈油多元醇为聚醚酯多元醇,且随着甲醇用量的增加,多元醇分子中羟基官能团的数量逐渐增加,但分子的主体结构没有变化。当醇油比为0.8∶1~1∶1时,棕榈油多元醇羟值约为130 mgKOH/g、黏度小于700 mPa·s,官能度大于2,且制备的包膜具有良好的热稳定性和耐水性。在无助剂包覆且包衣率为3%时,所制包膜尿素PCU3和PCU4氮素初期释放率约为7%,释放期为20天以上。试验证实包膜对种子萌发及作物生长没有不良影响。
    结论 最佳甲醇和棕榈油比范围为0.8∶1~1∶1,在此比例下的棕榈油多元醇羟值约为130 mgKOH/g,官能度大于2,黏度小于700 mPa·s,以其合成的棕榈油基可降解包膜材料的控释性能良好,棕榈油含量大于65%。

     

    Abstract:
    Objectives The physicochemical properties of vegetable oil polyols influence the microstructure and macroscopic properties of polyurethane materials. We changed the methanol dosage to adjust the hydroxyl value, viscosity and other indexes of palm oil-based polyols, to increase the properties of palm oil-based polyurethane coatings. The research was also designed to clarify the relationship between the physicochemical properties of polyols, polyurethane properties and the controlled release properties of fertilizers, to provide theoretical basis for optimizing coating quality and reducing cost of vegetable oil-based degradable coating fertilizer.
    Methods Palm oil with high saturation was used as feedstock, and the epoxidation/ring-opening method was used to synthesize four palm oil-based polyol samples by adjusting the adding ratios of methanol, denoted as POP1, POP2, POP3, and POP4. Then the four polyol samples were used to make controlled release urea PCU1, PCU2, PCU3, and PCU4 through in-situ reaction technology, respectively. The hydroxyl value, acid value, viscosity, molecular weight and functionality of palm oil-based polyols were measured, the microstructures of the palm oil-based polyols and the formed coating films were observed by FTIR, 1H NMR, SEM, and TG methods, respectively. The water absorption rate and cumulative N release rate of the coated urea samples were tested using weighing and water dissolving methods. The safety of the coating materials was evaluated by germination test.
    Results After adjusting methanol dosage, the hydroxyl values of the synthesized four POPs were 101−132 mgKOH/g, viscosities were 365−618 mPa·s, and the functionalities were 1.89−2.73. FTIR and 1H NMR showed that the POPs belonged to polyether ester polyols. With the increase of methanol ratio, the number of hydroxyl groups increased, but the molecular structure did not change. When the mass ratio of methanol and epoxidized palm oil was 0.8∶1−1∶1, the hydroxyl value of POP was about 130 mgKOH/g, the viscosity was less than 700 mPa·s, and functionality was more than 2. The resultant coating layers showed good thermal stability and water resistance. At the coating rate 3% (no accessory ingredient addition), the initial N release rates of PCU3 and PCU4 were about 7%, and the N release period lasted more than 20 days. The germination and safety experiment results showed that the coating materials did not cause side-effect on seed germination and crop growth.
    Conclusions The optimal mass ratio of methanol and epoxidized palm oil is in range of 0.8∶1 to 1∶1. Within the range, the synthesized palm oil-based polyols have hydroxyl value about 130 mgKOH/g, functionality more than 2, and viscosity less than 700 mPa·s. The resultant palm oil-based degradable coating materials show good controlled release performance, and the palm oil proportion in the coating materials could be as high as 65%.

     

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