聚（乙酰乙酸甲酯⁃新戊二醇二丙烯酸酯）的合成与反应动力学

doi:10.12422/j.issn.1672-6952.2026.01.002

摘要/Abstract

摘要：

以乙酰乙酸甲酯（MAA）和新戊二醇二丙烯酸酯（NPGDA）为原料，通过碱催化的迈克尔加成反应增长分子链，制备了线型聚合物聚（乙酰乙酸甲酯?新戊二醇二丙烯酸酯）（P(MAA?NPGDA)）；采用FTIR、¹H NMR、DSC、HPLC、GPC等技术对样品进行了表征和测试，考察了不同催化剂在不同温度下对反应过程中线型聚合物相对分子质量增长速率、放热速率和反应单体双键转化率的影响；以1,8?二氮杂双环[5.4.0]十一碳?7?烯（DBU）为催化剂，考察了反应温度、催化剂质量分数和n（MAA）/n（NPGDA）对线型聚合物相对分子质量增长速率的影响。结果表明，当反应温度为30~40 ℃、DBU质量分数为2%、n（MAA）/n（NPGDA）为1.00∶1.00时，P(MAA?NPGDA)的相对分子质量增长速率较为平稳，且最终能达到较高的相对分子质量水平。

关键词: 乙酰乙酸甲酯, 新戊二醇二丙烯酸酯, 线型高分子, 迈克尔加成, 动力学研究

Abstract:

With Methyl acetoacetate (MAA) and Neopentyl glycol diacrylate (NPGDA) as raw materials, a linear polymer, Poly (Methyl acetoacetate?Neopentyl glycol diacrylate) (P(MAA?NPGDA)),was prepared via a base?catalyzed Michael addition reaction to extend the molecular chain. The synthesized samples were characterized and analyzed by Fourier transform infrared spectroscopy (FTIR),proton nuclear magnetic resonance spectroscopy （¹H NMR）,differential scanning calorimetry（DSC）,high?performance liquid chromatography （HPLC） and gel permeation chromatography（GPC）. The effects of different catalysts on the relative molecular weight growth, heat release rate, and double bond conversion rate of monomers during the reaction were investigated at various temperatures. Furthermore, by using 1,8?Diazabicyclo[5.4.0]undec?7?ene (DBU) as the catalyst, the impacts of varying reaction temperatures, catalyst concentrations, and the ratio of n(MAA) to n(NPGDA) on the molecular weight growth of linear polymers were examined. Under the tested conditions, in a reaction temperature range of 30-40 ℃ with a DBU mass fraction of 2%, and a MAA?to?NPGDA monomer ratio of 1.00∶1.00, the growth rate of P(MAA?NPGDA) molecular weight was relatively stable, and the polymer ultimately reaches a relatively high relative molecular weight.

Key words: Methyl acetoacetate, Neopentyl glycol diacrylate, Linear high?molecular polymer, Michael addition, Dynamic studies

中图分类号:

TQ311

沈哲恒, 曾麟钦, 汪小宝, 王懿, 谢宇, 张洪吉. 聚（乙酰乙酸甲酯⁃新戊二醇二丙烯酸酯）的合成与反应动力学[J]. 辽宁石油化工大学学报, 2026, 46(1): 10-18.

Zheheng SHEN, Linqin ZENG, Xiaobao WANG, Yi WANG, Yu XIE, Hongji ZHANG. Synthesis and Reaction Kinetics Study of Poly (Methyl Acetoacetate⁃Neopentyl Glycol Diacrylate)[J]. Journal of Liaoning Petrochemical University, 2026, 46(1): 10-18.

图/表 12

图1 NPGDA和P(MAA?NPGDA)的红外光谱

Fig.1 FTIR spectra of NPGDA and P(MAA?NPGDA)

图2 NPGDA和P(MAA?NPGDA)的核磁共振氢谱

Fig.2 1H NMR spectra of NPGDA and P(MAA?NPGDA)

图3 不同催化剂在20 ℃下反应合成P(MAA?NPGDA)的GPC曲线

Fig.3 GPC curves of P(MAA?NPGDA) synthesized by different catalysts at 20 °C

图4 不同催化剂在60 ℃下反应合成P(MAA?NPGDA)的GPC曲线

Fig.4 GPC curves of P(MAA?NPGDA) synthesized by different catalysts at 60 °C

图5 不同催化剂对P(MAA?NPGDA)双键转化率的影响

Fig.5 Effect of different catalysts on the double bond conversion rate of P(MAA?NPGDA)

图6 P(MAA?NPGDA)在不同催化剂下的ln[1/(1-x)]?t曲线

Fig.6 ln[1/(1-x)]?t curves of P(MAA?NPGDA) under different catalysts

表1 P(MAA?NPGDA)聚合反应的动力学参数

Table 1 Kinetic parameters of the P(MAA?NPGDA) polymerization reaction

催化剂	n=1		n=2		n=3
催化剂	k₁/s^-1	R²	k₂/(L·mol^-1·s^-1)	R²	k₃/(L²·mol^-2·s^-1)	R²
TMG	2.59×10^-2	0.995	4.04×10^-2	0.977	1.30×10^-1	0.943
三乙胺	-1.10×10^-4	0.013	-1.10×10^-4	0.059	-2.20×10^-4	0.012
DBN	6.17×10^-3	0.958	7.15×10^-3	0.947	1.66×10^-2	0.954
DBU	9.00×10^-3	0.993	1.20×10^-2	0.989	3.18×10^-2	0.983
四丁基氢氧化铵	5.66×10^-4	0.376	6.36×10^-4	0.421	1.17×10^-3	0.335

图7 P(MAA?NPGDA)在不同催化剂下的DSC曲线

Fig.7 DSC curves of P(MAA?NPGDA) under different catalysts

图8 不同反应温度下以DBU为催化剂合成的P(MAA?NPGDA)的GPC曲线

Fig.8 GPC curves of P(MAA?NPGDA) synthesized with DBU as catalyst at different reaction temperatures

图9 反应单体和混合物反应前后的液相色谱图5 min的混合图谱 5 min的混合图谱

Fig.9 HPLC chromatograms of monomers and mixtures before and after reaction

图10 不同DBU质量分数下反应合成P(MAA?NPGDA)的GPC曲线

Fig.10 GPC chromatograms of P(MAA?NPGDA) synthesized by reaction at different DBU mass fractions

图11 不同n（MAA）/n（NPGDA）下合成P(MAA?NPGDA)的GPC曲线

Fig.11 GPC chromatograms of P(MAA?NPGDA) synthesized by reaction under different n(MAA)/n(NPGDA)

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