水可分散型松香基聚酯多元醇的制备及耐热性研究

Preparation and Heat Resistance of Water Dispersible Rosin-based Polyester Polyol

以马来海松酸(MPA)、新戊二醇(NPG)、三羟甲基丙烷(TMP)、间苯二甲酸(IPA)、己二酸(AA)、间苯二甲酸-5-磺酸钠(5-SSIPA)为原料,采用先分步熔融后溶剂回流法制得水可分散型松香基聚酯多元醇(WDRPP)。探讨了反应时间、催化剂用量、n(—OH)∶n(—COOH)和亲水单体用量对反应的影响,并利用傅里叶红外光谱(FT-IR)和^(13) C NMR对产物进行了表征。利用热重分析(TG)研究了WDRPP的耐热性,并采用Coats-Redfem法对WDRPP的热分解动力学试验数据进行拟合分析,得到动力学参数。结果表明,当反应时间为5.5 h(熔融反应3 h,溶剂回流2.5 h),催化剂用量为0.10%,n(—OH)∶n(—COOH)为1.4∶1,亲水单体用量为2.86%时,制备的WDRPP的热稳定性和WDRPP水分散体的稳定性最佳;WDRPP的最大失重速率温度(Tmax)为406.7℃、热解反应活化能为64.65 k J/mol,且热分解动力学曲线线性良好(R^2=0.997 3),表明WDRPP热分解过程符合一级反应动力学规律;FT-IR和^(13) C NMR的分析结果表明WDRPP制备成功。

Water dispersible rosin-based polyester polyol（ WDRPP） was prepared through the method of first fractional melting reaction and then reflux,using maleopimaric anhydride（ MPA）,neopentyl glycol（ NPG）,trimethylolpropane（ TMP）,isophthalic acid（ IPA）,adipic acid（ AA） and 5-sulfoiso-phtalic acid mono sodium salt（ 5-SSIPA） as raw materials. Effects of reaction time,the amount of catalyst,n（ —OH） ∶ n（ —COOH） and the amount of hydrophilic monomer on the reactions were investigated.The products were characterized by fourier transform infrared spectroscopy（ FT-IR） and13 C NMR. The heat resistance of WDRPP was studied using thermogravimetric analyzer（ TG）. The thermal degradation kinetic data were analyzed using Coats-Redfem method,and the kinetic parameters were obtained. The results showed that WDRPP with excellent thermostability and the WDRPP dispersion with good stability were obtained when reaction time was 5. 5 h（ melting reaction time of 3 h and reflux time of 2. 5 h）,the amount of catalyst was 0. 10%,n（ —OH） ∶ n（ —COOH） was 1. 4 ∶ 1,and the amount of hydrophilic monomer was 2. 86%,respectively. It was found that the temperature at maximum weight loss rate was 406. 7 ℃,the reaction activation energy of pyrolysis was 64. 65 k J / mol,and the linear curves of thermal degradation kinetics fitted well（ R2= 0. 997 3）. This indicated that the thermal degradation process of WDRPP followed the law of first-order kinetic reaction. FT-IR and13 C NMR resultsdemonstrated that WDRPP was prepared successfully.